metal-organic compounds Acta Crystallographica Section C Crystal Structure Communications

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4_英寸GaN_衬底MOCVD_外延高质量AlGaN

4英寸GaN衬底MOCVD外延高质量AlGaN/GaN HEMT材料研究分析高楠房玉龙* 王波张志荣尹甲运芦伟立陈宏泰牛晨亮（河北半导体所）摘要：本文对金属有机物化学气相淀积法在4英寸GaN衬底上生长出的高质量AlGaN/GaN HEMT外延材料进行了研究分析。

生长过程采用NH3/H2混合气体及H2交替通入的方法对衬底表面进行了预处理，阻隔了界面杂质的扩散。

得益于衬底与外延的高度晶格匹配，GaN材料的螺位错密度降低到1.4×107cm-2，刃位错密度降低到3.0×106cm-2；非接触霍尔测试仪结果显示二维电子气迁移率为2159 cm2/V·s ，说明制备的材料晶体质量高且电学性能优异。

此外，由于衬底与外延之间不存在热失配，使用拉曼光谱仪发现同质外延的GaN E2（TO）峰位与衬底的E2（TO）峰位完全重合，表明同质外延过程中无应力应变产生。

关键词：GaN衬底，AlGaN/GaN HEMTStud y of High-quality AlGaN/GaN HEMT Homo-epitaxial Material on4-inch GaN Substrate by MOCVDGAO Nan FANG Yu-long* WANG Bo ZHANG Zhi-rong YIN Jia-yun LU Wei-liCHEN Hong-tai NIU Chen-liang（Hebei Semiconductor Research Institute）Abstract:High-quality AlGaN/GaN HEMT homo-epitaxial material grown on 4-inch GaN homo-substrate by metal-organic chemical vapor deposition (MOCVD) was studied in this paper. An alternation gas model of ammonia/ hydrogen (NH3/H2) mixed gas and H2 gas was employed to thermal treatment of GaN homo-substrate to prevent the spread of impurities. Due to the match of lattices, the density of screw dislocation was as low as 1.4×107cm-2 and the density of edge dislocation reached 3.0×106cm-2. The contactless Hall test results showed that the AlGaN/GaN HEMT material had a two-dimensional electron gas (2DEG) mobility of 2159 cm2/V•s, indicating that the homo-epitaxial AlGaN/GaN HEMT material has high quality and good electrical performance. In addition, thanks to the absent thermal mismatch during the growth, the Raman spectrum test manifested that the peak positions of E2-high for GaN homo-substrate and the epitaxial material were totally coincident, showing that there was no strain in the homo-epitaxial growth.Keywords: GaN substrate, AlGaN/GaN HEMT作者简介：高楠，硕士，工程师，主要研究方向为宽禁带半导体材料生长及相关技术。

金属有机

Chemical Engineering Journal 171 (2011) 517–525Contents lists available at ScienceDirectChemical EngineeringJournalj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /c ejSynthesis,characterization and hydrogen adsorption on metal-organic frameworks Al,Cr,Fe and Ga-BTBDipendu Saha ∗,Renju Zacharia,Lyubov Laﬁ,Daniel Cossement,Richard ChahineInstitut de recherche sur l’hydrogène,Universitédu Québec àTrois-Rivières,Trois-Rivières,QC G9A 5H7,Canadaa r t i c l ei n f oArticle history:Received 21February 2011Received in revised form 7April 2011Accepted 8April 2011Keywords:Metal-organic framework (MOF)BTB ligand Pore textureSpeciﬁc surface area Hydrogen adsorptiona b s t r a c tBenzenetribenzoate (BTB)ligand is combined with four trivalent metals,Al,Cr,Fe and Ga by solvothermal synthesis to form four different metal-organic frameworks (MOFs),abbreviated as M-BTB,where M stands for the metal.Each of the MOFs is characterized with pore texture,scanning electron microscopic images (SEM),X-ray diffraction (XRD),Fourier transform infra-red spectroscopy (FT-IR)and thermogravimetric analysis (TGA).Pore texture reveals the highest BET surface area belongs to Al-BTB (1045m 2/g)and decreases in the order of Cr >Fe >Ga.Hydrogen adsorption at 77K and up to ambient pressure indicates that Al-BTB adsorbs highest amount of H 2(0.98wt.%)and decreases in the same order as the speciﬁc surface areas.High pressure H 2adsorption at room temperature (298K)and pressure up to 80bar reveals that Fe-BTB adsorbs highest amount of hydrogen (0.51wt.%or 2.75g L −1,absolute)and the adsorption amount decreases in the order of Cr >Al >Ga.© 2011 Elsevier B.V. All rights reserved.1.IntroductionMetal-organic frameworks (MOFs)are highly promising adsor-bents because of their very high speciﬁc surface area,tunable pore size and case-speciﬁc tailoring of basic molecular architec-ture leading to the large and selective adsorption capacities of several gas molecules.A large volume of MOFs has been reported in the literature;most of them were synthesized and decorated accordingly with an aim towards gas storage [1–3],separation [4],heterogeneous catalysis [5],drug delivery [6]or molecular sens-ing [7].Topologically,all the MOFs consist of metal centers,more precisely known as secondary building units (SBUs)connected with each other by the organic molecules,commonly known as organic linkers [8].Different types of metals have been employed and examined for the structure forming capacity of MOFs;typical examples are zinc [9–15,28],copper [16,17],chromium [18–20],aluminum [21,22],iron [23,24],scandium [25],manganese [26],zirconium [27],vanadium [29]or cadmium [42].Organic linker is probably the far most important part in tai-loring the architecture of metal-organic frameworks.The linker molecule plays the role to tune the pore size and speciﬁc sur-face area of the MOFs.Most versatile usages of different organic molecules as linkers were noticed in synthesizing different species of IRMOFs where zinc was employed as part of secondary build-ing units [8,28].Benzenedicarboxylic acid (BDC)or terephthalic∗Corresponding author.Tel.:+18652422221;fax:+18655768424.E-mail address:dipendus@ (D.Saha).acid is most common in synthesizing different species of MOFs,including MOF-5[9,13,28],MIL-53(Cr,Al or Fe)[19,29]or MIL-101[20,30,31].However,the reported large surface area and the maxi-mum gas (H 2and CO 2)uptake is observed for benzenetribenzoic acid (BTB)as organic linker that formed metal-organic frame-work,MOF-177with zinc as SBU former [10–12,14,15,33–35].Besides hydrogen and carbon dioxide,methane [36],nitrous oxide [36]and carbon monoxide [37]adsorption was also exam-ined on MOF-177.In recent time,Furukawa et al.incorporated few other ligands,like 4,4 ,4 -(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE),4,4 ,4 -(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate (BBC)or biphenyl-4,4 -dicarboxylate (BPDC)that demonstrated even larger surface area than BTB containing ligands [38].Apart from the usage of pure or only one type of ligand,employing more than one ligand to form a single MOF was reported recently.Koh et al.[39]combined BDC and BTB lig-ands in different proportions to form different species of MOFs and it was reported that between the ratio of 6:4and 5:5of BDC over BTB,a new type of mesoporous MOF was generated and has been named as UMCM-1.Saha and Deng [40]also gen-erated two types of hybrid MOFs consisting of BDC and BTB by employing two different solvents,DMF (N,N,dimethylformaide)and DEF (N,N,diethylformaide).In other work,Koh et al.[41],syn-thesized the hybrid MOF (UMCM-2)with the combination of BTB and thieno[3,2-b]thiophene-2,5-dicarboxylate (T 2DC)in 1:1ratio,that possesses the BET surface area of more than 5000m 2/g.Klein et al.[43]synthesized the hybrid mesoporous MOF DUT-6with BTB and NDC (2,6-naphthalenedicarboxylate)in 3:2mole ratio that possesses high pore volume of 2.02cm 3/g.Despite the ubiquitous1385-8947/$–see front matter © 2011 Elsevier B.V. All rights reserved.doi:10.1016/j.cej.2011.04.019518 D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Table 1Synthesis conditions of the metal-organic frameworks.MOF identityMetal saltsSalts amount (g)BTB amount (g)Thermal conditionsAl-BTB Al(NO 3)3·9H 2O 0.1710.290◦C,24h Cr-BTB Cr(NO 3)3·9H 2O 0.1820.290◦C,24h Fe-BTB Fe(NO 3)3·9H 2O 0.2700.280◦C,3days Ga-BTBGa(NO 3)3·x H 2O0.2550.2100◦C,24hevidence that BTB ligand could provide high surface area and gas adsorption properties,it was not employed to form MOFs with any other metal,till today.In this work,we combined BTB ligand with four differ-ent trivalent metals,aluminium,chromium,iron and gallium to form four types of metal-organic frameworks.Each type of MOF was performed materials characterization with pore tex-ture,density measurement,scanning electron microscopy (SEM),Fourier-transform infra-red (FT-IR)spectra,thermogravimetric analysis (TGA)and X-ray diffraction to reveal the identity of the crystals.Hydrogen adsorption measurement was performed at 77K and room temperature to examine the hydrogen sorption capacity of those MOFs.2.Experimental methods2.1.Synthesis of Al,Cr,Fe and Ga-BTBAll metal-organic frameworks of this present work were syn-thesized by solvothermal technique.In general,the corresponding metal salts or the metal precursors were dissolved in 25mL ethanol,where as the BTB ligand was dissolved in 10mL N,N-dimethylformamide (DMF)followed by mixing the two solutions and subjecting to thermal treatment.For Ga-BTB,both the pre-cursor and the ligand were dissolved in 35mL of DMF as the Ga precursor was sparingly soluble in ethanol.The exact identity of metal precursor,amounts of reagents and the thermal conditions are revealed in details in Table 1.After the thermal treatment,the crystals were separated from the solution and washed twice with DMF in order to remove any unreacted reagent.Finally,the DMF treated samples were washed several times with chloroform min-imize the DMF level within the crystals and stored inside glovebox under argon atmosphere in closed container.2.2.Materials characterizationsThe materials characterizations techniques employed for each sample include pore textural properties,density measurement,Fourier-transform infra-red spectroscopy (FT-IR),thermo gravi-metric analysis (TGA),scanning electron microscopy (SEM)and X-ray diffraction technique.The pore textural properties were calculated by nitrogen adsorption–desorption study at liquid nitrogen temperature (77K)and pressure up to 1bar in Micromeritics ASAP 2020instrument.The pore textural properties BET surface area and pore size distribu-tion by density functional theory (DFT)were obtained by analyzing the nitrogen adsorption and desorption isotherms with the built-in software in the ASAP 2020surface area and porosity analyzer.The adsorbent samples were degassed ex-situ at 373K for 24h toa bcd10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.2Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )Fig.1.N 2adsorption–desorption plot of Al-BTB (a),Cr-BTB (b),Fe-BTB (c),Ga-BTB (d).D.Saha et al./Chemical Engineering Journal171 (2011) 517–525519remove the guest molecules from the samples before the nitrogen adsorption measurements.The FT-IR spectra of the samples were measured in Thermo-Scientiﬁc Nicolet iN10-MX FT-IR chemical imaging microscope within the wave numbers of4000–800cm−1.The sample prepa-rations include grinding and mixing with KBr followed by pelletization before introducing to the laser.Scanning electron microscopy images(SEM)images were recorded by employing JEOL JSM-5500instrument by using an accelerating voltage of18kV.The thermogravimetric analysis(TGA)was performed in Perkin Elmer TGA7Instrument.The temperature ramp rate employed for this study was10◦C/min up to800◦C in an inert gas(Ar)ﬂow.The X-ray data were recorded in Bruker D8Advance X-ray diffractometer with Cu K␣emission( =1.54056˚A).For each sample,the XRD scan was performed from2◦to75◦with0.02◦width and1s count time.Pro-cessing of all diffraction data including structure reﬁnement was performed using JADE8+software supplied by Materials Data Inc. (Livermore,CA,USA).2.3.Hydrogen adsorption measurementHydrogen adsorption at low(up to1bar)pressure and at77K was measured volumetrically in ASAP2020instrument.About 50mg of each of the sample was used in this experiment.The adsor-bent sample was degassed under a vacuum and at373K for24h before the hydrogen adsorption measurement.Ultra-high purity hydrogen(Praxair Inc.)was introduced into a separate gas port of the adsorption unit for the hydrogen adsorption measurements.The high pressure hydrogen adsorption was measured in Sieverts-type volumetric apparatus,built and calibrated in our laboratory.About100mg of sample was introduced within the sample container and it was subjected to room temperature out-gassing at10−3Torr by employing a turbomolecular pump before any measurement.The skeleton density of the samples were mea-sured by admitting ultra-high purity helium gas(Praxair Inc.) in to the system and performing the density measurement at ambient temperature and equilibrium pressure less than20bar in order to minimize the effect of helium adsorption.The tem-perature and pressure of the gas were monitored by employing calibrated Guildline9540digital platinum resistance temperature detector(accuracy=±0.01◦C)and Paroscientiﬁc740digiquartz high accuracy digital pressure gauge(accuracy=0.01%at f.s.).The real gas densities were obtained from the NIST-12standard ref-erence database.The sample skeleton densities were calculated from the linear regression of sample mass versus gas density plots. Hydrogen adsorption isotherms were measured by using ultra-high purity hydrogen gas(Praxair Inc.).The excess gas adsorption was measured at room temperature(298K)and pressure up to80bar. To estimate the order of uncertainties that might arise from our adsorption measurement,we performed a skeleton density and hydrogen adsorption measurement of similar masses of activated carbon AX-21,whose adsorption characteristics are well-known. The maximum uncertainty of our experiments was found to be not more than±3%.The measured leak rate on this system is practically negligible:10−6MPa/s with He gas at4MPa and room temperature. Leak measured using Mathewson Leak hunter plus8066yielded no leak with hydrogen gas at5MPa and room temperature(minimum detectable leak of the instrument is8.1×10−6mL s−1of hydrogen).3.Results and discussions3.1.Materials characterizations3.1.1.Pore texture and densityThe pore texture properties including BET speciﬁc surface area and pore size distribution were calculated from nitrogen Table2Pore texture properties.MOF identity BET SSA(m2g−1)Bulk density, b(g cm−3)Skeleton density,s(g cm−3)Al-BTB10450.30 1.72Cr-BTB5520.54 1.96Fe-BTB3620.33 1.17Ga-BTB620.29 2.865adsorption–desorption plot by employing the built-in software of Micromeritics ASAP2020porosity and surface area analyzer(shown in Fig.1(a)–(d)).The bulk density was measured in ASTM standard D2854-96where as the skeleton density was measured by helium expansion experiment at ambient temperature.The pore texture and density values of all the samples are shown in details in Table2. It is observed that the highest BET SSA(1045m2g−1)were achieved for aluminum(Al)sample.The surface areas decrease in the order of Cr>Fe>Ga.The pore size distribution calculated by density func-tional theory(DFT)for all the samples are shown in Fig.2(a)and (b)for differential and cumulative pore volume,respectively.It is observed almost all the MOFs possess very narrow distribution in the microporous region,though majority of the pore volumes con-tribute in the mesopore region.Al-BTB possesses two peaks,8.58˚A and11.79˚A though the large pore volume arises from pores in the region of120˚A.Cr-BTB shows the presence of pores in8.58˚A and 12.69˚A but also shares large pore volume in less than100˚A.Fe-BTB is having very low pore volume in microporous region of8˚A and 12.69˚A but having very large pore volume in the range of160˚A. Amongst all the MOFs,Ga-BTB shows the lowest available pore volume,narrow micropore in12.69˚A,but larger pore volume in <200˚A.It is also clear that these MOFs posses the micropore width in the range of8–12˚A along with large mesopores which may arise due to possible crystalline defects.The total pore volume is highestabPore width (Å)Differentialporevolume(cc/g-Å)Pore width (Å)Cumulativeporevolume(cc/g)Fig.2.(a)Differential pore size distribution by DFT theory.(b)Cumulative pore size distribution by DFT theory.520 D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Fig.3.Scanning electron images,Al-BTB (a),Cr-BTB (b),Fe-BTB (c)and Ga-BTB (d).for Al-BTB followed by Cr-BTB,Fe-BTB and Ga-BTB as observed in Fig.2(b).It is noticeable that the speciﬁc surface areas of all the samples are lower than MOF-177[11,12]or other BTB contain-ing hybrid MOFs [39,41,43].Most probably,the presence of two or more interwoven three-dimensional nets within MOF structures lowered their porosity as observed in the case of PCN-6[44]or MOF-14[Cu 3(BTB)2][45].However,the speciﬁc surface areas of Al-BTB is higher than several other mesoporous MOFs reported till today,like JUC-48[42].The Cr-BTB sample attained the largest bulk density of 0.54g cm −3.For all the remaining samples,the bulk density lies in the close region of 0.29(Ga)to 0.33g cm −3(Fe).The skeleton den-sity was observed to be highest for Ga sample (2.86g cm −3).Lower values of skeleton were densities achieved for Al (1.72g cm −3),Fe (1.17g cm −3)and Cr (1.96g cm −3)based samples.3.1.2.Scanning electron microscopy (SEM)The scanning electron microscopic (SEM)images for Al,Fe,Cr and Ga samples are shown in Fig.3(a)–(d),respectively.All the images were taken after outgassing the MOFs at elevated tem-perature.The morphology of the crystallites is not quite well distinguishable for all samples,most probably because of the lower magniﬁcation power of our SEM microscope.For Ga sample,the crystallites look quite close to the hexagonal proﬁle with size range from 0.5␮m in the face to 0.13␮m in width.The crystallites of Fe sample resemble cubic or orthogonal nature with average size 0.33␮m.The exact morphology of Al and Cr samples was not possi-ble to determine with the present SEM image,however,the average size of the crystals could be approximated as 0.1–0.15␮m for Cr and 0.07–0.13␮m for Al samples.3.1.3.X-ray diffractionThe X-ray diffraction patterns of the four samples are shown in Fig.4.It is observed that the sharpest peak of all the MOFsisAngle(2θo)I n t e n s i t y (c o u n t s )Fig.4.X-ray diffraction patterns.D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525521I n t e n s i t y (a .u .)located at around 6◦followed by a shorter peak at an angle of 11◦.There are also some broad peaks located at higher angles of all the samples.Al and Cr-BTB possess the broad peak at an angle 19–20◦,where as Ga sample shows two small but broad peaks at 35◦and 64◦.Al-BTB possesses a broad peak at an angle of 44◦and a small peak at the shorter angle of 3.4◦.For Fe-BTB,two broader peak formations are also located at 33◦–34◦and 44◦–45◦.Unlike MOF-177or UMCM-1,none of our samples shows the largest peak at 4◦–5◦(MOF-177[12])or 2◦–3◦(UMCM-1[39]),however,all the samples possess the largest peak at 6◦–7◦,similar to that of UMCM-2[41].It is also noticeable that almost all of the peaks of each of the pattern are quite broad in nature accompanied by quite heavy noise and low intensity.Most probably,very thin layer of chloro-form was still present in the inter-lattice spaces of crystals that prohibited the penetration of X-ray within it as described by Saha and Deng [32].The wide pore opening of the mesoporous mate-rials may also caused the partial collapse of the crystalline lattice after the removal guest species during the outgassing phase at ele-vated temperature,as suggested by Koh et al.[39]or observed in the XRD pattern of the mesoporous MOF composed of Al III with one or bidentate ligand comprising of six membered aro-matic rings [46].Due to the poor peak proﬁle and possible lack in accuracy in the overall pattern,we did not attempt to index the peaks and hence did not report the crystal phase identiﬁcation data.3.1.4.FT-IR spectraThe FT-IR spectra of the four metal-organic frameworks are pro-vided in Fig.5.The overall patterns are in quite well agreement with other BTB containing MOFs,reported elsewhere [14,47].The sharp peak at 1400cm −1region is attributed to the symmetric stretching of C O bond that belongs to the carboxylate group of the BTB ligand,where as the peak at 1600cm −1is originated from the asymmetric stretching of the same bond [47].The few weak peaks at 1300–1000cm −1can be attributed to the in-plane bend-ing vibrations of aromatic C–H bonds and the remaining smaller angle peaks (1000–800cm −1)could be contributed by the out of plane bending vibration of C–H bonds [14,47].The C C stretch-ing vibration from the benzene ring of the BTB ligand appears as a weak peak at 1520–1570cm −1.Few weak peaks starting after 1600cm −1till 2000cm −1are attributed to the ﬁrst overtone of in-plane and out of plane vibrations of C–H bonds of BTB ligand,where as the second overtone appears at 2600–2100cm −1.Very broad and weak peak formation in the region of 3000cm −1is attributed to the aromatic C–H stretching of the BTB ligand [14].Finally,the absence of any strong peak at 1700cm −1provides the clear indi-0102030405060708090100ab0200400600800w t .%-8-7-6-5-4-3-2-100100200300400500600700800Tempe rature (o C)D i f f e r e n t i a l -w t .% (d w t .%/d t )Fig.6.Thermogravimetric analysis (TGA),linear form (a)and differential form (b).cation of absence of any free carboxylic acid in the MOF samples[14].3.1.5.Thermogravimetric analysis (TGA)The thermogravimetric plots in linear and differential form are shown in Fig.6(a)and (b).From the differential plot,the losses in weight can be localized in the three discrete regions of 50–100◦C,150–250◦C and 500–600◦C.Very minute loss is observed around in the ﬁrst region of 50–100◦C (1–2wt.%)that can be contributed to the desorption of adsorbed gas from their pore spaces.In the sec-ond region,150–250◦C,the cause of mass loss is attributed to the removal of guest species,mostly N,N dimethylformamide (DMF).For Cr,Fe and Ga based samples,the loss is in this region is lim-ited to 6–7wt.%unlike Al species that suffered a signiﬁcant loss of 19wt.%.This higher loss is a clear indication of larger occupancy of guests within the Al based MOF that could provide better pore texture if it were outgassed at elevated temperature and/or with elongated time period.The ﬁnal region of loss at 500–600◦C can be attributed to the disintegration of framework,i.e.,the decomposi-tion of BTB ligand itself.From the differential plot,the loss can be quantiﬁed approximately as 31,15,49and 34wt.%for Al,Cr,Fe and Ga based MOFs,respectively.The ﬁnal residue amount was within 30–45wt.%for all the samples that can be attributed to the oxides of the corresponding metals.The weight loss due to the decompo-sition BTB ligand is much smaller compared to the possible overall proportion of BTB in the MOF resulting in quite higher ﬁnal residue than expected for a metal oxide.Most probably,there was a sig-niﬁcant amount of carbon deposition,originated from the organic ligand,on the metal oxides as the TGA measurement was performed in an inert atmosphere.522D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Pressure (Torr)H 2 a d s o r b e d (w t .%)Fig.7.Low pressure hydrogen adsorption isotherms.4.Hydrogen adsorption properties4.1.Low pressure hydrogen adsorptionThe low pressure hydrogen adsorption for all the MOFs were measured at liquid nitrogen temperature (77K)and pressure up to 800Torr in ASAP 2020instrument.The hydrogen adsorption isotherms are shown in Fig.7.All the isotherms are typically type-I according to IUPAC classiﬁcations.The highest adsorption is exhib-ited by Al-MOF,around 0.98wt.%,followed by Cr (0.76wt.%),Fe(0.67wt.%)and Ga (0.36wt.%).It is observed that the hydrogen uptake at ambient pressure range was dictated by BET speciﬁc sur-face area as the hydrogen adsorption amount decreases exactly in the same as BET SSA (Al >Cr >Fe >Ga)as observed in Table 2.The lower hydrogen uptake of all of these samples compared to MOF-177or several other BTB containing MOFs can be attributed to the lower porosity of the materials that is probably caused by the interwoven 3D nets within the structures as described earlier.All the hydrogen adsorption isotherms were modeled by four well-known equations,Langmuir,Freundlich,Sips (Langmuir–Freundlich)and Toth models [12,13].The Langmuir isotherm can be written as:q =a m bP 1+bP(1)where q (wt.%)is the adsorbed hydrogen amount,p is the hydro-gen pressure (Torr),a m (wt.%)is the monolayer adsorption capacity and b (Torr −1)is the other Langmuir isotherm equation parameter.Both equation parameters can be determined from the slope and intercept of a linear Langmuir plot of (1/q )versus (1/p ).Freundlich isotherm is given by:q =kP 1/n(2)where k and n are the Freundlich isotherm equation parameters that can be determined by the slope and intercept of ln P versus ln q plot.The Sips (Langmuir–Freundlich)model can be written asq =a m bP (1/n )1+bP (1/n )(3)where a m ,b and n are equations constants.a cb dPressue (Torr)H 2 a d s o r b e d (w t %)00.10.20.30.40.50.60.70.8800700600500400300200100Pressure (Torr)H 2 a d s o r b e d (w t .%)00.10.20.30.40.50.60.70.8Pressure (Torr)H 2 a d s o r b e d (w t .%)Pressure (Torr)H 2 a d s o r b e d (w t .%)Fig.8.Isotherm model ﬁtting,Al-BTB (a),Cr-BTB (b),Fe-BTB (c)and Ga-BTB (d).D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525523Table 3Parameters of isotherm model ﬁtting.Isotherm modelModelparameters Parametervalues (Al-BTB)Parameter values (Cr-BTB)Parameter values (Fe-BTB)Parameter values (Ga-BTB)ARE%(Al-BTB)ARE%(Cr-BTB)ARE%(Fe-BTB)ARE%(Ga-BTB)Langmuir modela m 1.1580.82510.7120.378 1.4561.631.5940.622b0.0060.0090.0100.016Freundlich modelk 0.0660.0840.0910.082 1.7010.8030.4870.367n2.4272.9833.2974.401Sips modela m 1.533 2.473 2.526 1.2880.2510.4140.2390.257b 0.0120.0260.0300.059n1.3322.3582.6723.483Toth model˛T 5.340 4.972 4.919 5.2680.8290.3270.1630.257k T 2.595 1.347 1.0250.463t0.2450.1810.1560.086The Toth model can be given byq =˛T p (k T +p t )(1/t )(4)where ˛T ,k T and t are Toth equation constants.All the equation parameters of Sips and Toth model can be calculated by non-liner regression techniques.The degree of model ﬁtting was compared by the absolute relative error (ARE)percent,calculated asARE%=Nn =1|x exp −x mod |N×100%(5)where x exp is the experimental point,x mod is the modeling point and N is the number of points in the isotherm.These parameters are given in Table 3and model ﬁtting plots are shown in Fig.8(a)–(d)for Al,Cr,Fe and Ga samples,respectively.ARE values conﬁrmed that Sips model ﬁt better for Al-BTB,however,Toth model ﬁts best for the rest of MOFs.4.2.High pressure hydrogen adsorptionThe high pressure adsorption of four MOFs at room tempera-ture (298K)and pressure up to 80bar is shown in Fig.9(a)and (b)for gravimetric and volumetric capacities,respectively.The excess adsorption amount was directly obtained from the instru-ment shown as the symbols in the plots.Assuming the adsorbed the gas density is equivalent to the liquid density of the same species (hydrogen),the absolute adsorption amount can be calculated as [11,12]m abs =m excess1−( (T,P )/ (l ))(6)where (T ,P )is density of the adsorptive gas (hydrogen)at the particular temperature and pressure and (l )is the density of the same gas in the liquid phase.The absolute adsorption was repre-sented as continuous curve in the plots.It is clearly observed that the Fe-BTB performs highest hydrogen uptake both gravimetri-cally (abs:0.51wt.%,excess:0.465wt.%)and volumetrically (abs:2.75g L −1,excess:2.51g L −1).The hydrogen uptake amounts of the remaining samples lie in the similar range,however,minute observation reveals that the uptake capacity decreases in the order of Cr (0.42wt.%,1.38g L −1)>Al (0.25wt.%,0.85g L −1)>Ga (0.27wt.%,0.8g L −1),all absolute amount.It is also noticeable that the hydrogen adsorption increases linearly with pressure similar to that of many other types of MOFs,which are caused by the poor adsorbate–adsorbent interactions at the ambient temperature level.It is evident that the hydrogen adsorption amounts at elevated pressure and at ambient temperature were not controlled by the pore texture properties unlike the adsorption at ambient pressureabPressure (bar)H 2 a d s o r b e d (w t .%)Pressure (bar)H 2 a d s o r b e d (g L -1)Fig.9.High pressure hydrogen adsorption,gravimetric adsorption amount (a)andvolumetric uptake amount (b).and 77K temperature which are quite obvious due to the associ-ated mesoporosity of these MOFs.The signiﬁcant higher adsorption by Fe-BTB over the rest of the MOFs is most probably caused by the possible open or unsaturated metal sites that could be created during the evacuation step by the elimination of one or more sol-vent molecules from the MOF cavities [48].The unsaturated metal sites can increase the electrostatic attraction between hydrogen and partial charges on metal-organic framework atoms thereby dominating the key adsorption mechanism.5.ConclusionIn this work,we synthesized four metal-organic frameworks by the incorporation of benzenetribenzoate (BTB)ligand with four。

金属有机化合物

基
如：CH2SiMe3 或CH2Ph
② “阻断”β－H转移：吸电子基或π酸作为配体
例如：Ti(CH3)4在－50℃时也有些分解，而Ti(bipy)（CH3）2直到30 ℃都稳定存在。
M
N(CH3)2 CH2
N
2RP
PR2
2 HC
C H2
M
H2 C
CH2
M
N(CH3)2
C H2
H.Schmidbauer et al., Angew,Chem.,Int.Ed.,17,126(1978);Acc.Chem.Res.,8,62(1975)
③大多数配合物都服从有效原子序数规则。
2.羰基化合物的制备
(1)金属粉末与CO直接作用如四羰基合镍、五羰基合铁的合成。金属粉末必须是新鲜还原出来的处于非常活化的状态才行。
Ni＋4CO 常温常压 Ni(CO)4(m.p.－25℃) △ Ni＋4CO
Fe＋5CO 493K , 20MPa Fe(CO)5
①金属与CO之间的化学键很强。如在Ni(CO)4中，Ni－ C键能为147 kJ·mol－1，这个键能值差不多与I－I键能(150 kJ·mol－1)和C－O单键键能(142 kJ·mol－1)值相差不多。
②在这类配合物中, 中心原子总是呈现较低的氧化态( 通常为0，有时也呈较低的正氧化态或负氧化态)。氧化态低使得有可能电子占满d－MO, 从而使M→L的电子转移成为可能。
2、实际应用：广泛的应用，最突出的是用作催化剂
目前，金属有机化学已成为无机化学、有机化学、结构化学、配位催化以及生物化学等多种学科相互渗透、共同研究的重要领域。
4. 金属有机化合物的特点
成键类型：是经典的化学键理论无法说明的

ferrocenecompounds.xxxix

metal-organic compoundsm328#2003International Union of CrystallographyDOI:10.1107/S0108270103011703Acta Cryst.(2003).C 59,m328±m330Ferrocene compounds.XXXIX.11-FerrocenylisochromaneMario Cetina,a Senka akovicÂ,b Vladimir Rapic Âb *and Amalija GolobicÏc aFaculty of Textile Technology,University of Zagreb,Pierottijeva 6,HR-10000Zagreb,Croatia,b Laboratory of Organic Chemistry,University of Zagreb,Faculty of Food Technology and Biotechnology,Pierottijeva 6,HR-10000Zagreb,Croatia,and cLaboratory of Inorganic Chemistry,Faculty of Chemistry and Chemical Technology,University of Ljubljana,PO Box 537,SI-1001Ljubljana,Slovenia Correspondence e-mail:*************Received 14April 2003Accepted 27May 2003Online 22July 2003In the title compound,[Fe(C 5H 5)(C 14H 13O)],the plane of the heterocyclic ring is almost perpendicular to the plane of the substituted cyclopentadienyl ring,and the heterocyclic ring adopts a half-chair conformation.The conformation of the nearly parallel cyclopentadienyl (Cp)rings [the dihedral angle between their planes is 2.7(1) ]is almost halfway between eclipsed and staggered,and the rings are mutually twisted by about 19.4(2) (mean value).The mean lengths of the CÐC bonds in the substituted and unsubstituted cyclopentadienylring are 1.420(2)and 1.406(3)AÊ,respectively,and the FeÐC distances range from 2.029(2)to 2.051(2)AÊ.The phenyl and unsubstituted cyclopentadienyl rings are involved in CÐH ÁÁÁ%interactions,with intermolecular H ÁÁÁcentroiddistances of 2.85and 3.14AÊfor CÐH ÁÁÁ%(Ph),and 2.88A Êfor CÐH ÁÁÁ%(Cp).In two of these interactions,the CÐH bond points towards one of the ring bonds rather than towards the ring centroid.In the crystal structure,the CÐH ÁÁÁ%interactions connect the molecules into a three-dimensional framework.CommentOptically active ferrocene derivatives are widely employed as chiral ligands in asymmetric reactions,and there is continuing interest in the development of ef®cient procedures for the preparation of these derivatives in enantiopure forms (Gonsalves &Chen,1995;Bolm et al.,1998;Pioda &Togni,1998;Perea et al.,1999).Ferrocene derivatives exhibiting centro-and planar chirality are very convenient substrates forbiotransformations (KoÈllner et al.,1998;Richards &Locke,1998;Schwink &Knochel,1998;Patti &Nicolosi,1999;akovicÂet al.,2003).In the course of our research on enzyme-catalyzed resolution of centrochiral ferrocene compounds,racemic 2-( -hydroxyferrocenyl)benzenethanol and 1-ferro-cenylisochromane,(I),were prepared by reduction of methyl2-(ferrocenoyl)benzeneacetate ( akovicÂ,2000).The molecular structure of (I)is the ®rst reported structure to contain an isochromanyl group attached to the ferrocenyl moiety (Fig.1).Moreover,the Cambridge Structural Database (Allen,2002)lists only three structures containing an iso-chromanyl group at all (Yamato et al.,1984;Unterhalt et al.,1994;Eikawa et al.,1999).The heterocyclic six-membered ringActa Crystallographica Section CCrystal Structure CommunicationsISSN0108-2701Figure 2Part of the crystal structure of (I),showing the formation of (010)sheets built from C14ÐH14A ÁÁÁCg 1i and C18ÐH18ÁÁÁCg 2ii interactions (Cg 1and Cg 2are the centroids of rings C12/C13/C16±C19and C6±C10,respectively).CÐH ÁÁÁ%interactions are indicated by dashed lines.[Symmetry codes:(i)x ,12Ày ,z À12;(ii)1+x ,y ,1+z.]Figure 1A view of (I),with the atom-numbering scheme.Displacement ellipsoids for non-H atoms are drawn at the 20%probability level.1Part XXXVIII:Cetina et al.(2003).adopts a distorted half-chair conformation,in which atoms O1and C15are 0.426(1)and À0.348(2)AÊfrom the plane of the other ring atoms (C11±C14);the C11ÐC12ÐC13ÐC14torsion angle is 2.4(2) .The bond lengths in the heterocyclic and fused phenyl rings (Table 1)mostly agree with the equivalent bond lengths in the structures of 1,1H -oxybis(iso-chromane)(Eikawa et al.,1999)and (S )-1-(phenyl)ethyl-ammonium (S )-isochromane-1-carboxylate (Unterhalt et al.,1994).The exception is the C12ÐC13bond,which is shorter($0.04AÊ)in the latter structure.Heterocyclic ring atoms O1,C11and C15and cyclopentadienyl (Cp)ring atom C1lie in the same plane,the C15ÐO1ÐC11ÐC1torsion angle being 178.95(14) .The dihedral angle between the mean plane of these four atoms and the C1±C5Cp ring is 47.8(1) .Furthermore,the plane of the heterocyclic ring is almost perpendicular to the plane of the C1±C5ring and is parallel to the plane of the fused phenyl ring.The corresponding dihedral angles are 87.3(1)and 4.0(1) .The exocyclic C2ÐC1ÐC11bond angle is larger than the C5ÐC1ÐC11angle (Table 1).The Cp rings are planar and almost parallel to each other [the dihedral angle between their planes is 2.7(1) ],and the FeÐC distances are in the range2.034(2)±2.051(2)AÊfor the substituted (C1±C5)and 2.029(2)±2.049(2)AÊfor the unsubstituted (C6±C10)ring,the average values being 2.042(2)and 2.038(2)AÊ,respectively.The CÐC bonds are slightly longer in the substituted ring than in the unsubstituted ring [1.410(3)±1.429(2)versus 1.397(3)±1.414(3)AÊ],and the bond angles in both rings range from 107.52(15)to 108.33(18) .The geometry of the ferrocenyl moiety agrees well with the structures of ferrocene (Seiler &Dunitz,1979)and of theferrocene derivatives we have reported previously (Cetina et al.,2002,2003).The main conformational difference was observed in the orientation of the Cp rings.In (I),the rings are twisted from an eclipsed conformation by 19.4(2) (mean value).The values of the corresponding CÐCg 3ÐCg 2ÐC pseudo-torsion angles (Cg 3and Cg 2are the centroids of the C1±C5and C6±C10rings,respectively),de®ned by joining two eclipsing Cp C atoms through the ring centroids,range from 19.0(2)to 19.7(2) .The conformation is almost exactly halfway between eclipsed and staggered,as demonstrated by the C1ÐCg 3ÐCg 2ÐC9torsion angle of 163.4(1) .This angle would be 180 for a staggered conformation and 144 for a fully eclipsed conformation.The centroids of the Cp rings are almost equidistant from the Fe atom;the FeÐCg 3and FeÐCg 2distances are 1.647(1)and 1.650(1)AÊ,respectively,while the Cg 3ÐFeÐCg 2angle is 178.2(1) .There are a number of CÐH ÁÁÁ%interactions (Table 2and Fig.2).Atom H14A of the heterocyclic ring is positioned almost perpendicularly above the phenyl-ring centroid (Cg 1)of the adjacent molecule.The six relevant H ÁÁÁC distances fallin the narrow range 3.06±3.28AÊ,and the H ÁÁÁCg i distance is signi®cantly shorter than any of the H ÁÁÁC distances[symmetry code:(i)x ,12Ày ,z À12;Table 2].The CÐH ÁÁÁ%interaction between phenyl atom H18and the unsubstituted Cp ring exhibits a completely different geometry.The H18ÁÁÁC7ii distance is shorter than the H ÁÁÁCg ii distance [symmetry code:(ii)1+x ,y ,1+z ].The second shortest H ÁÁÁC contact is that to atom C6,and the CÐH bond points towards the C6ÐC7bond of the Cp ring rather than towards the ring centroid (Cg 2).Similarly,the longest interaction,C5ÐH5ÁÁÁCg 1iii [symmetry code:(iii)1Àx ,Ày ,2Àz ],points towards the C12ÐC13bond.Both the H5ÁÁÁC12iii and the H5ÁÁÁC13iii contacts are shorter than the H ÁÁÁCg iii distance.The molecules linked by these CÐH ÁÁÁ%interactions build a three-dimensional framework (Fig.3).ExperimentalNaBH 4(253mg,6.7mmol)was added gradually to a solution of methyl 2-(ferrocenoyl)benzeneacetate (326mg,0.9mmol)in a mixture of EtOH and Et 2O (1:1v /v ;5ml).The mixture was re¯uxed for 2h and worked up in the usual manner.Separation by preparative thin-layer chromatography on silica gel (Merck,Kieselgel 60HF 254)yielded 2-( -hydroxyferrocenyl)benzeneethanol (237mg;yield 78%)and orange crystals of 1-ferrocenylisochromane (57mg;yield 20%;m.p.365±366K).Single crystals of the title compound were obtained by slow evaporation from a cyclohexane solution at room tempera-ture.IR (CH 2Cl 2,cm À1):)3081(w )and 3020(w )(CÐH,ferrocene),2942(m )(CÐH,aliphatic),1278(m )(CÐOÐC);1H NMR (DMSO,p.p.m.): 7.18(d ,1H,H16),7.12(d ,1H,H17),7.14(d ,1H,H18),7.16(d ,1H,H19),4.23(s ,5H,unsubstituted ferrocene ring),4.13±4.20(m ,4H,substituted ferrocene ring),3.97(m ,1H,H15A ),3.77(m ,1H,H15B ),2.78(m ,2H,H14),5.58(s ,1H,H11);13C NMR (DMSO,p.p.m.): 137.29(C12),132.91(C13),128.5(C17),126.25(C18),125.98(C16),125.36(C19),90.21(C1),73.63(C11),68.62(unsub-stituted ferrocene ring),68.56±66.31(substituted ferrocene ring),61.55(C15),27.99(C14).Acta Cryst.(2003).C 59,m328±m330Mario Cetina et al.[Fe(C 5H 5)(C 14H 13O)]m329metal-organic compoundsFigure 3Part of the crystal structure of (I),showing the cyclic motif generated by the C5ÐH5ÁÁÁCg 1iii interaction (Cg 1is the centroid of ring C12/C13/C16±C19),which links the (010)sheets into a three-dimensional framework.CÐH ÁÁÁ%interactions are indicated by dashed lines,and the unit-cell box has been omitted for clarity.[Symmetry code:(iii)1Àx ,Ày ,2Àz .]metal-organic compoundsm330Mario Cetina et al.[Fe(C 5H 5)(C 14H 13O)]Acta Cryst.(2003).C 59,m328±m330Crystal data[Fe(C 5H 5)(C 14H 13O)]M r =318.18Monoclinic,P 21a ca =11.5053(2)A Êb =18.5095(3)A Êc =7.1941(1)AÊ =106.933(1)V =1465.62(4)AÊ3Z =4D x =1.442Mg m À3Mo K radiationCell parameters from 3411re¯ections =2.6±27.5 "=1.02mm À1T =293(2)K Prism,orange0.80Â0.40Â0.15mm Data collectionNonius KappaCCD area-detector diffractometer 9and 3scansAbsorption correction:multi-scan (DENZO±SMN ;Otwinowski &Minor,1997)T min =0.630,T max =0.85716885measured re¯ections3334independent re¯ections 2662re¯ections with I >2'(I )R int =0.064 max =27.4 h =À14314k =À23323l =À939Re®nementRe®nement on F 2R [F 2>2'(F 2)]=0.030wR (F 2)=0.076S =1.033334re¯ections 190parametersH-atom parameters constrainedw =1/['2(F 2o )+(0.0341P )2+0.3545P ]where P =(F 2o +2F 2c )/3(Á/')max =0.001Á&max =0.25e A ÊÀ3Á&min =À0.23e AÊÀ3All H atoms were included in calculated positions as riding atoms,with SHELXL 97(Sheldrick,1997)defaults viz.CÐH =0.93AÊfor aromatic H atoms,0.98AÊfor methine H atoms,and 0.97A Êfor methylene H atoms.For all H atoms,the isotropic displacement parameters were set at 1.2times the equivalent anisotropic displacement parameters of the attached non-H atoms.Data collection:COLLECT (Nonius,2000);cell re®nement:DENZO±SMN (Otwinowski &Minor,1997);data reduction:DENZO±SMN ;program(s)used to solve structure:SHELXS 97(Sheldrick,1997);program(s)used to re®ne structure:SHELXL 97(Sheldrick,1997);molecular graphics:PLATON (Spek,2003);soft-ware used to prepare material for publication:SHELXL 97.The re¯ection data were collected at the Faculty of Chem-istry and Chemical Technology,University of Ljubljana,Slovenia.We acknowledge with thanks the ®nancial contri-bution of the Ministry of Education,Science and Sport of the Republic of Slovenia (grant Nos.X-2000and PS-511-103),which made the purchase of the apparatus possible.Supplementary data for this paper are available from the IUCr electronic archives (Reference:GD1251).Services for accessing these data are described at the back of the journal.ReferencesAllen,F.H.(2002).Acta Cryst.B 58,380±388.Bolm,C.,MunÄiz-Ferna Ândez,K.,Seger,A.,Raabe,G.&Gunther,K.(1998).Chem.63,7860±7867.Cetina,M.,Hergold-BrundicÂ,A.,Nagl,A.,Jukic Â,M.&Rapic Â,V .(2003).Struct.Chem.14,289±293.Cetina,M.,MrvosÏ-Sermek,D.,Jukic Â,M.&Rapic Â,V .(2002).Acta Cryst.E 58,m676±m678.akovicÂ,S.(2000).PhD thesis,University of Zagreb,Croatia. akovicÂ,S.,Lapic Â,J.&Rapic Â,V .(2003).Biocatal.Biotransform.In the press.Eikawa,M.,Sakaguchi,S.&Ishii,Y.(1999).Chem.64,4676±4679.Gonsalves,K.E.&Chen,X.(1995).Ferrocenes ,edited by A.Togni &T.Hayashi,ch.10,pp.497±527.Weinheim:VCH.KoÈllner,C.,Pugin,B.&Togni,A.(1998).J.Am.Chem.Soc.120,10274±10275.Nonius (2000).COLLECT.Nonius BV ,Delft,The Netherlands.Otwinowski,Z.&Minor,W.(1997).Methods in Enzymology ,Vol.276,Macromolecular Crystallography ,Part A,edited by C.W.Carter Jr &R.M.Sweet,pp.307±326.New York:Academic Press.Patti,A.&Nicolosi,G.(1999).Tetrahedron :Asymmetry ,10,2651±2654.Perea,J.J.A.,Lotz,M.&Knochel,P .(1999).Tetrahedron :Asymmetry ,10,375±384.Pioda,G.&Togni,A.(1998).Tetrahedron :Asymmetry ,9,3903±3910.Richards,C.J.&Locke,A.(1998).Tetrahedron :Asymmetry ,9,2377±2407.Schwink,L.&Knochel,P .(1998).Chem.Eur.J.4,950±968.Seiler,P .&Dunitz,J.D.(1979).Acta Cryst.B 35,2020±2032.Sheldrick,G.M.(1997).SHELXS 97and SHELXL 97.University ofGoÈttingen,Germany.Spek,A.L.(2003).J.Appl.Cryst.36,7±13.Unterhalt,B.,Krebs,B.,Lage,M.&Nocon,B.(1994).Arch.Pharm.327,799±804.Yamato,M.,Hashigaki,K.,Kokubu,N.&Nakato,Y.(1984).J.Chem.Soc.Perkin Trans.1,pp.1301±1304.Table 2Hydrogen-bonding geometry (AÊ, ).Cg 1and Cg 2are the centroids of rings C12/C13/C16±C19and C6±C10,respectively.D ÐH ÁÁÁA D ÐH H ÁÁÁA D ÁÁÁA D ÐH ÁÁÁA C14ÐH14A ÁÁÁCg 1i 0.97 2.85 3.627(2)138C18ÐH18ÁÁÁCg 2ii 0.93 2.88 3.660(2)142C18ÐH18ÁÁÁC7ii 0.93 2.86 3.760(3)163C18ÐH18ÁÁÁC6ii 0.93 3.03 3.874(3)151C5ÐH5ÁÁÁCg 1iii 0.93 3.14 3.984(2)152C5ÐH5ÁÁÁC12iii 0.93 2.98 3.840(2)154C5ÐH5ÁÁÁC13iii0.933.023.949(2)177Symmetry codes:(i)x Y 12Ày Y z À12;(ii)1 x Y y Y 1 z ;(iii)1Àx Y Ày Y 2Àz .Table 1Selected geometric parameters (AÊ, ).O1ÐC111.4236(19)O1ÐC15 1.432(2)C1ÐC11 1.503(2)C11ÐC12 1.523(2)C12ÐC16 1.388(2)C12ÐC13 1.397(2)C13ÐC19 1.392(3)C13ÐC14 1.504(3)C14ÐC15 1.501(3)C16ÐC17 1.384(3)C17ÐC18 1.380(3)C18ÐC19 1.379(3)C11ÐO1ÐC15110.39(13)C2ÐC1ÐC11127.61(14)C5ÐC1ÐC11124.78(14)O1ÐC11ÐC1109.37(13)O1ÐC11ÐC12111.64(13)C1ÐC11ÐC12112.14(13)C13ÐC12ÐC11119.77(14)C12ÐC13ÐC14120.38(16)C15ÐC14ÐC13111.24(15)O1ÐC15ÐC14110.04(15)。

211262186_Cu-MOF_材料的合成及其对有机小分子的荧光识别

第52卷第5期辽宁化工 Vol.52，No. 5 2023年5月 Liaoning Chemical Industry May，2023基金项目：① 2021年贵州省大学生创新创业训练计划项目（国家级）（项目编号：202110667029）；②2021年贵州省大学生创新创业训练计划项目（省级）（项目编号：202110667005）；③贵州省教育厅2021年度市（州）普通本科高校青年科技人才成长项目（项目编号：黔教合KY 字[2022]036号）。

收稿日期： 2022-09-29Cu -MOF 材料的合成及其对有机小分子的荧光识别文勇武，江创，张玉蝶，熊琴，赵永婷*（安顺学院，贵州安顺 561000）摘要：通过水热法合成了一例Cu-MOF 材料（化合物1）。

单晶衍射分析表明化合物1属于单斜晶系，空间群为P21/c ，晶胞参数a = 7.309 6，b =10.917 4，c =14.114 5，α=90，β=91.497，γ=90 。

对化合物1进行荧光性能研究，荧光结果分析表明，在260 nm 的激发波长下，化合物1在390 nm 处有强的荧光发射峰。

并研究了化合物1对不同有机溶剂分子的荧光特性。

通过荧光光谱测试表明，化合物1在乙醇溶液中表现出荧光猝灭现象，对乙醇溶剂具有良好的荧光识别性能。

关键词：Cu-MOF 材料；有机溶剂；荧光；识别中图分类号：TQ201 文献标识码： A 文章编号： 1004-0935（2023）05-0627-04金属有机框架材料(MOFs ），又称为配位聚合物材料，是由金属离子或者金属团簇与有机配体通过配位键自组装连接而成的一维、二维或三维结构[1]。

金属中心的配位模式、金属半径大小以及配体的配位齿的数目、配位点间的间距、配体的给体基团性质等都会对整个自组装过程起决定性作用。

合成MOFs 材料的方法主要有水热法、溶剂热法、微波合成法、电化学法和其他方法等[2-4]，水热合成至今已有100多年历史，目前已经发展成金属有机框架材料合成的主要途径之一。

Acta Cryst. (2013). C69, 1017–1021

One-dimensional Cu I and Ag I ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazoleLiu-cheng Gui,*Guang-ming Liang,Hua-hong Zou and Zhong HouSchool of Chemistry and Chemical Engineering,Guangxi Normal University,Guilin 541004,People’s Republic of ChinaCorrespondence e-mail:guiliucheng2000@ Received 25May 2013Accepted 19July 2013The title complexes,poly[[bis[ 2-2-ethyl-1-(pyridin-3-ylmeth-yl)-1H -benzimidazole- 2N 1:N 3]copper(I)]tetraﬂuoroborate acetonitrile monosolvate],{[Cu(C 15H 15N 3)2]BF 4ÁCH 3CN}n ,(I),and poly[[bis[ 2-2-ethyl-1-(pyridin-3-ylmethyl)-1H -benz-imidazole- 2N 1:N 3]silver(I)]perchlorate methanol monosol-vate],{[Ag(C 15H 15N 3)2]ClO 4ÁCH 3OH}n ,(II),are isostructural and exhibit one-dimensional ladder-like structures in which each asymmetric unit contains one metal ion (Cu +or Ag +),two 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazole (bep)ligands,one counter-anion (tetraﬂuoroborate or perchlorate)and one interstitial molecule (acetonitrile or methanol).Each metal ion exhibits a distorted tetrahedral coordination geometry consisting of two pyridyl and two benzimidazole N atoms from four distinct ligands.Two metal ions are linked by two bep ligands to form a centrosymmetric 18-membered M 2(bep)2metallacycle,while adjacent M 2(bep)2metallacycles are further interlinked by another two bep ligands resulting in a ladder-like array.In the extended structure,four adjacent ladder-like arrays are connected together through C—H ÁÁÁF,O—H ÁÁÁO and C—H ÁÁÁO hydrogen bonds between bep ligands,solvent molecules and counter-anions into a three-dimensional supramolecular structure.Keywords:crystal structure;inorganic–organic coordination polymers;2-ethyl-1-(pyridin-3-ylmethyl)benzimidazole ligand;crystal engineering.1.IntroductionCurrently,the rational design and synthesis of inorganic–organic coordination polymers have attracted considerable attention due to the intriguing variety of architectures and topologies that can be produced,and the potential applica-et al.,2007;Murray et al.,2009;Zhang,Liu et al.,2010;Zhang,Zhang et al.,2013).Many factors,such as the metal centres (as nodes),organic linkers (as building blocks),solvent molecules,temperature,templates,counter-anions etc .,can affect the ﬁnal architectures (Tong et al.,1998;Ferey et al.,2005;Bradshaw et al.,2005;Uemura et al.,2006;Zhang,Wang et al.,2010).In particular,the structure of the ligand and the coordination mode of the metal ion play key roles in determining the nature of the coordination polymer (Liu et al.,2007;Lee et al.,2008;Zheng et al.,2009).There has been much interest and progress recently in the crystal engineering of supramolecular architectures organized and sustained by means of bis-heterocyclic chelating or brid-ging ligands with pyridine,pyrazine,imidazole and diazoles;and 4,40-bipyridine and its derivatives have been the most frequently used bridging ligands for constructing interesting grid or chain-like coordination polymers (Hartshorn et al.,1998;Li et al.,2007;Zhai et al.,2011).Recently,pyridyl/benzimidazolyl-based ligands with a freely rotatable methyl-ene (–CH 2–)juncture between the pyridyl ring and the benzimidazole moiety have attracted considerable attention for two main reasons:(i)they possess ﬂexibility owing to the presence of the methylene (–CH 2–)spacer;(ii)they can act as 2-bridging ligands via the pyridyl and benzimidazole N atoms.In previous studies,N -(pyridin-2-ylmethyl)-1H -benzi-midazole (2-pb-m),N -(pyridin-3-ylmethyl)-1H -benzimidazole (3-pb-m)and N -(pyridin-4-ylmethyl)-1H -benzimidazole (4-pb-m)have been used to create one-dimensional double-helical chains,and two-and three-dimensional networks with d 10metals (Wang et al.,2009;Huang et al.,2006).To extend the study of these types of ligands,an ethyl group was introduced into the 2-position of the benzimidazole system,giving the new ligand 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazole (bep),which is expected to produce inter-esting structures mediated by the steric and electronic effects of the ethyl group.In this study,two isostructural compounds,{[Cu(bep)2]BF 4ÁCH 3CN}n ,(I),and {[Ag(bep)2]ClO 4ÁCH 3-OH}n ,(II),were obtained by the reaction of bep and [Cu(CH 3CN)4]BF 4or AgClO 4.These isostructural complexes metal-organic compoundsActa Crystallographica Section CCrystal Structure CommunicationsISSN0108-27012.Experimental2.1.Synthesis and crystallizationBep was synthesized according to the method reported by Huang et al.(2006).For the preparation of (I),a solution of [Cu(CH 3CN)4]BF 4(0.05mmol)in a mixture of CH 3CN (3ml)and N ,N -dimethylformamide (DMF,3ml)was added to bep (0.1mmol).A yellow solution formed and was ﬁltered.Diethyl ether was diffused slowly into the solution and,after several days,yellow block-shaped crystals suitable for X-ray diffrac-tion analysis had formed (yield 60%).Elemental analysis calculated for C 32H 33BCuF 4N 7:C 57.71,H 4.99,N 14.72%;found:C 57.48,H 5.12,N 14.34%.For the preparation of (II),a solution of AgClO 4(0.05mmol)in a mixture of CH 3OH (3ml)and DMF (3ml)was added to bep (0.1mmol).A yellow solution formed and was ﬁltered.Diethyl ether was diffused slowly into the solution and,after several days,yellow block-shaped crystals suitable for X-ray diffraction analysis had formed (yield 80%).Elemental analysis calculated for C 31H 34AgClN 6O 5:C 52.15,H 4.80,N 11.77%;found:C 52.01,H 4.96,N 11.46%.2.2.RefinementCrystal data,data collection and structure reﬁnement details are summarized in Table 1.In both structures,all C-bound H atoms were placed in idealized positions,withC—H =0.93A˚and U iso (H)=1.2U eq (C)for aromatic H atoms,˚In order to make the reﬁnement of the acetonitrile solvent molecules in (I)and the methanol solvent molecules in (II)fully anisotropic,all their C,N and O atoms were subjected to a ‘rigid bond’restraint (DELU instruction in SHELXL97;Sheldrick,2008),i.e.the mean-square displacements in the direction of the corresponding bonds were restrained to beequal within an effective standard uncertainty of 0.005A˚2.In addition,within this same set of atoms,those closer than 1.7A˚were restrained with an effective standard uncertainty ofmetal-organic compoundsTable 1Experimental details.(I)(II)Crystal dataChemical formula [Cu(C 15H 15N 3)2]BF 4ÁC 2H 3N[Ag(C 15H 15N 3)2]ClO 4ÁCH 4O M r666.00713.96Crystal system,space group Triclinic,P 1Triclinic,P 1Temperature (K)298298a ,b ,c (A˚)9.3674(4),12.5367(6),13.3150(7)9.560(7),12.946(10),13.849(11) , , ( )89.912(2),72.786(2),84.599(1)90.163(10),108.773(9),95.518(9)V (A ˚3)1486.42(12)1614(2)Z22Radiation type Mo K Mo K (mm À1)0.800.76Crystal size (mm)0.68Â0.21Â0.150.60Â0.20Â0.18Data collection DiffractometerBruker SMART CCD area-detector diffractometerBruker SMART CCD area-detector diffractometerAbsorption correction Multi-scan (SADABS ;Bruker,2001)Multi-scan (SADABS ;Bruker,2001)T min ,T max0.614,0.8900.850,0.860No.of measured,independent and observed [I >2 (I )]reﬂections 14603,6748,600410939,7140,5396R int0.0200.018(sin / )max (A˚À1)0.6490.670ReﬁnementR [F 2>2 (F 2)],wR (F 2),S 0.047,0.141,1.090.044,0.118,1.02No.of reﬂections 67487140No.of parameters 408400No.of restraints 209H-atom treatmentH-atom parameters constrained H-atom parameters constrained Á max ,Á min (e A˚À3) 2.18,À0.910.78,À0.51Computer programs:SMART (Bruker,2001),SAINT (Bruker,2007),SHELXS97(Sheldrick,2008),SHELXL97(Sheldrick,2008)and SHELXTL (Sheldrick,2008).Figure 1A view of (I),showing the atom-labelling scheme.Displacement ellipsoids are drawn at the 30%probability level.H atoms are shown as small spheres of arbitrary radii and have been omitted from symmetry-0.005A˚2to have the same U ij components(SIMU instruc-tion).The reﬁnement of the H atoms of the acetonitrile solvent molecules in(II)required the inclusion of inter-molecular restraints to avoid convergence to unreasonable intermolecular HÁÁÁH distances.The intermolecular HÁÁÁH shortest contact distances were restrained to2.30A˚.Bond distances involving non-H atoms in these groups were also subjected to distance restraints.3.Results and discussionAs compounds(I)and(II)are isostructural,only the structure of(I)is described in detail here.The asymmetric unit of(I) contains one Cu I atom,two coordinated bep ligands,one tetraﬂuoroborate counter-anion and one lattice acetonitrile molecule(Fig.1).The Cu I centre adopts a distorted tetra-hedral coordination geometry consisting of two pyridyl(py)N atoms[N6i and N3ii;symmetry codes:(i)Àx+1,Ày,Àz+1; (ii)x+1,y,z]and two benzimidazole(Bm)N atoms(N1and N4),which are from four distinct ligands.The Cu—N Bm bond lengths[2.018(2)and2.041(2)A˚]are distinctly shorter than those of Cu—N py[2.108(2)and 2.155(2)A˚]due to the benzimidazole group being more electron-rich,and hence a stronger donor,than the pyridyl group.The same results have been observed by others(Su et al.,1999).The bond angles around each Cu I centre(Table2)are within the expected range for similar complexes(Su et al.,1999).In(II),the Ag—N Bm[2.230(3)and2.257(3)A˚]and Ag—N py[2.397(3) and2.443(3)A˚]bond lengths are all longer than the Cu—N bonds in(I)due to the Ag+radius being larger than that of Cu+(Huang et al.,2006).Two metal ions are bridged by two 2-bep ligands,forming an18-membered M2(bep)2metallacycle with an MÁÁÁM separation of7.933(1)A˚for(I)and8.167(5)A˚for(II) (Fig.2).C—HÁÁÁ interactions between ethyl H atoms of one ligand and the benzimidazole system of another molecule further stabilize the metallacycle[C—HÁÁÁ (centroid)= 3.086A˚for(I),with atom C24as donor,via atom H24C,to the C16A–C21A ring at(Àx+1,Ày,Àz+1),and3.303A˚for(II), with atom C24as donor,via atom H24B,to the C16A–C21A ring at(Àx,Ày,Àz+1)].The metallacycles can be viewed as the rungs of the ladder,which are further connected by two bep ligands to form one-dimensional ladder-like arrays,with MÁÁÁM separations of9.368(1)A˚for(I)and9.560(7)A˚for (II).In contrast with other analogues,the title compounds exhibit one-dimensional ladder-like coordination polymers with metallacycle units,which may be the result of two factors: (i)the ligand possessingﬂexibility owing to the presence of a methylene(–CH2–)spacer between the pyridyl ring and the benzimidazole moiety;(ii)the steric and electronic effect of the ethyl group introduced into the2-position of benzimida-zole.Thus,the present work once again emphasizes themetal-organic compoundsFigure2(a)The one-dimensional ladder-like chain of(I)and(II),(b)the18-membered M2(bep)2metallacycle and(c)a schematic view of the one-dimensional ladder-like chain.The Cu atoms and organic linker ligands are represented by red balls and curved lines,respectively.Table2Selected geometric parameters(A˚, )for(I).Cu1—N1 2.018(2)Cu1—N6i 2.108(2) Cu1—N4 2.041(2)Cu1—N3ii 2.155(2) N1—Cu1—N4126.94(9)N1—Cu1—N3ii118.24(8) N1—Cu1—N6i101.41(8)N4—Cu1—N3ii99.80(9) N4—Cu1—N6i104.97(9)N6i—Cu1—N3ii102.48(9)Table3Hydrogen-bond geometry(A˚, )for(I).D—HÁÁÁA D—H HÁÁÁA DÁÁÁA D—HÁÁÁA C10—H10AÁÁÁF2iii0.97 2.55 3.505(4)169C10—H10BÁÁÁF40.97 2.39 3.353(3)175C19—H19AÁÁÁF3iv0.93 2.53 3.412(3)158important role played by both the metal centres and organic linkers on theﬁnal structures of coordination complexes.In the crystal packing,four adjacent ladder-like arrays are connected through C—HÁÁÁF,O—HÁÁÁO and C—HÁÁÁO sional supramolecular structure.In(I),the tetraﬂuoroborate anion connects four adjacent ladder-like arrays through C19—H19AÁÁÁF3,C10—H10AÁÁÁF2and C10—H10BÁÁÁF4hydro-gen bonds(Table3),forming the three-dimensional super-molecular structure(Fig.3a).In(II),the perchlorate anion acts in the same manner through C10—H10AÁÁÁO3,C23—H23AÁÁÁO4,O5—H5BÁÁÁO1and C31—H31CÁÁÁO3hydrogen bonds(Table5and Fig.3b).This work is supported by National NSF of China(No. 21201045)and NSF of Guangxi Province(No.2013-GXNSFBA019039).Supplementary data for this paper are available from the IUCr electronic archives(Reference:WQ3040).Services for accessing these data are described at the 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C69, 1017-1021 [doi:10.1107/S0108270113019963]One-dimensional Cu I and Ag I ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazoleLiu-cheng Gui, Guang-ming Liang, Hua-hong Zou and Zhong HouComputing detailsFor both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).(1) Poly[[bis[µ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ2N1:N3]copper(I)] tetrafluoroborate acetonitrile monosolvate]Crystal data[Cu(C15H15N3)2]BF4·C2H3N M r = 666.00Triclinic, P1Hall symbol: -P 1a = 9.3674 (4) Åb = 12.5367 (6) Åc = 13.3150 (7) Åα = 89.912 (2)°β = 72.786 (2)°γ = 84.599 (1)°V = 1486.42 (12) Å3Z = 2F(000) = 688D x = 1.488 Mg m−3Mo Kα radiation, λ = 0.71073 Åθ = 2.2–25.0°µ = 0.80 mm−1T = 298 KBlock, yellow0.68 × 0.21 × 0.15 mmData collectionBruker SMART CCD area-detector diffractometerRadiation source: fine-focus sealed tube Graphite monochromatorω scansAbsorption correction: multi-scan (SADABS; Bruker, 2001)T min = 0.614, T max = 0.89014603 measured reflections 6748 independent reflections 6004 reflections with I > 2σ(I) R int = 0.020θmax = 27.5°, θmin = 3.2°h = −11→12k = −16→16l = −17→17RefinementRefinement on F2Least-squares matrix: full R[F2 > 2σ(F2)] = 0.047 wR(F2) = 0.141S = 1.096748 reflections408 parameters 20 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(F o2) + (0.0762P)2 + 1.632P] where P = (F o2 + 2F c2)/3(Δ/σ)max = 0.001Δρmax = 2.17 e Å−3Δρmin = −0.91 e Å−3Special detailsGeometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)x y z U iso*/U eqCu10.42937 (3)0.24036 (2)0.32103 (2)0.02427 (12)N10.2425 (2)0.25010 (17)0.27419 (17)0.0219 (4)N20.0736 (2)0.30988 (17)0.19341 (17)0.0224 (4)N3−0.4284 (2)0.36926 (18)0.28324 (19)0.0264 (5)N40.4437 (2)0.20740 (18)0.46810 (17)0.0236 (4)N50.3778 (2)0.18863 (17)0.64224 (17)0.0219 (4)C10.1811 (3)0.1626 (2)0.24431 (19)0.0203 (5)C20.2104 (3)0.0532 (2)0.2570 (2)0.0237 (5)H2A0.27810.02790.29250.028*C30.1360 (3)−0.0165 (2)0.2153 (2)0.0262 (5)H3A0.1537−0.08980.22310.031*C40.0341 (3)0.0211 (2)0.1613 (2)0.0258 (5)H4A−0.0128−0.02810.13300.031*C50.0017 (3)0.1294 (2)0.1492 (2)0.0242 (5)H5A−0.06640.15450.11400.029*C60.0762 (3)0.1991 (2)0.19250 (19)0.0211 (5)C70.1748 (3)0.3359 (2)0.2426 (2)0.0218 (5)C80.2027 (3)0.4474 (2)0.2649 (2)0.0287 (6)H8A0.16130.49690.22230.034*H8B0.30990.45270.24630.034*C90.1310 (4)0.4775 (3)0.3803 (3)0.0410 (7)H9A0.15510.54770.39420.061*H9B0.16850.42650.42250.061*H9C0.02400.47750.39740.061*C10−0.0160 (3)0.3819 (2)0.1425 (2)0.0258 (5)H10A−0.02280.34660.07950.031*H10B0.03440.44610.12140.031*C11−0.1724 (3)0.4132 (2)0.2146 (2)0.0246 (5)C12−0.2054 (3)0.5024 (2)0.2813 (3)0.0348 (6)H12A−0.13170.54750.28060.042*C13−0.3498 (3)0.5242 (2)0.3495 (3)0.0390 (7)H13A−0.37420.58420.39450.047*C14−0.4565 (3)0.4553 (2)0.3491 (3)0.0334 (6)H14A−0.55190.46900.39660.040*C15−0.2892 (3)0.3507 (2)0.2169 (2)0.0241 (5)H15A−0.26910.29270.16960.029*C160.5692 (3)0.2153 (2)0.5031 (2)0.0224 (5)C170.7172 (3)0.2302 (2)0.4468 (2)0.0292 (6)H17A0.74710.23420.37390.035*C180.8175 (3)0.2389 (2)0.5038 (2)0.0316 (6)H18A0.91670.24900.46840.038*C190.7736 (3)0.2327 (2)0.6133 (2)0.0305 (6)H19A0.84370.24080.64900.037*C200.6278 (3)0.2147 (2)0.6704 (2)0.0265 (5)H20A0.59860.20930.74320.032*C210.5286 (3)0.20541 (19)0.6119 (2)0.0213 (5)C220.3333 (3)0.1911 (2)0.5532 (2)0.0225 (5)C230.1791 (3)0.1729 (2)0.5521 (2)0.0287 (6)H23A0.16140.20330.48930.034*H23B0.10650.20950.61270.034*C240.1566 (3)0.0542 (3)0.5543 (2)0.0361 (7)H24A0.05740.04540.55090.054*H24B0.16870.02480.61820.054*H24C0.22940.01760.49510.054*C250.2879 (3)0.1741 (2)0.7503 (2)0.0268 (5)H25A0.18350.17390.75250.032*H25B0.29500.23450.79340.032*C260.3357 (3)0.0720 (2)0.7968 (2)0.0230 (5)C270.3125 (3)0.0668 (2)0.9045 (2)0.0325 (6)H27A0.27030.12670.94800.039*C280.3528 (4)−0.0283 (3)0.9463 (2)0.0364 (7)H28A0.3378−0.0334 1.01830.044*N70.6571 (12)0.7019 (7)−0.0088 (9)0.223 (5)C310.6053 (9)0.6234 (8)0.0375 (6)0.163 (4)C320.5185 (11)0.5398 (8)0.0993 (5)0.329 (9)H32A0.49360.55760.17290.493*H32B0.57770.47180.08460.493*H32C0.42790.53600.08020.493*B10.1334 (4)0.7004 (3)0.1088 (3)0.0328 (7)F10.2692 (3)0.7337 (2)0.1087 (2)0.0653 (7)F20.0565 (4)0.77528 (18)0.06303 (19)0.0726 (8)F30.0482 (2)0.69078 (16)0.21312 (14)0.0425 (4)F40.1548 (2)0.60215 (14)0.05601 (14)0.0417 (4)C290.4154 (3)−0.1153 (2)0.8800 (2)0.0294 (6)H29A0.4434−0.17860.90880.035*N60.4381 (2)−0.11307 (18)0.77614 (17)0.0240 (4)C300.3979 (3)−0.0203 (2)0.73583 (19)0.0216 (5)H30A0.4125−0.01790.66370.026*Atomic displacement parameters (Å2)U11U22U33U12U13U23Cu10.01949 (17)0.02608 (18)0.03104 (19)0.00154 (12)−0.01450 (13)−0.00219 (12)N10.0167 (9)0.0234 (10)0.0271 (10)0.0003 (8)−0.0096 (8)−0.0004 (8) N20.0161 (9)0.0239 (10)0.0299 (11)−0.0011 (8)−0.0115 (8)0.0022 (8)N30.0185 (10)0.0249 (11)0.0380 (12)−0.0013 (8)−0.0121 (9)0.0007 (9)N40.0146 (9)0.0292 (11)0.0289 (11)−0.0011 (8)−0.0099 (8)−0.0011 (8) N50.0154 (9)0.0236 (10)0.0273 (11)0.0013 (8)−0.0083 (8)−0.0017 (8) C10.0152 (10)0.0244 (12)0.0219 (11)−0.0006 (9)−0.0070 (9)−0.0017 (9) C20.0184 (11)0.0272 (12)0.0265 (12)0.0003 (9)−0.0091 (9)0.0022 (9)C30.0225 (12)0.0240 (12)0.0313 (13)−0.0022 (10)−0.0068 (10)0.0008 (10) C40.0201 (11)0.0290 (13)0.0295 (13)−0.0060 (10)−0.0081 (10)−0.0028 (10) C50.0171 (11)0.0315 (13)0.0255 (12)−0.0018 (10)−0.0087 (9)0.0004 (10) C60.0149 (10)0.0244 (12)0.0237 (11)0.0000 (9)−0.0059 (9)0.0017 (9)C70.0141 (10)0.0242 (12)0.0277 (12)0.0008 (9)−0.0080 (9)−0.0012 (9) C80.0227 (12)0.0249 (13)0.0428 (15)−0.0024 (10)−0.0161 (11)0.0018 (11) C90.0428 (17)0.0322 (15)0.0492 (18)0.0005 (13)−0.0168 (15)−0.0122 (13) C100.0187 (11)0.0287 (13)0.0336 (13)−0.0021 (10)−0.0133 (10)0.0078 (10) C110.0188 (11)0.0204 (11)0.0391 (14)−0.0017 (9)−0.0155 (10)0.0074 (10) C120.0233 (13)0.0239 (13)0.062 (2)−0.0019 (10)−0.0206 (13)−0.0026 (12) C130.0274 (14)0.0240 (13)0.067 (2)0.0042 (11)−0.0185 (14)−0.0142 (13) C140.0201 (12)0.0294 (14)0.0506 (17)0.0054 (10)−0.0128 (12)−0.0085 (12) C150.0188 (11)0.0237 (12)0.0334 (13)−0.0006 (9)−0.0136 (10)0.0010 (10) C160.0166 (11)0.0251 (12)0.0291 (12)−0.0006 (9)−0.0128 (10)0.0006 (9)C170.0182 (12)0.0389 (15)0.0330 (14)−0.0041 (11)−0.0112 (10)0.0081 (11) C180.0182 (12)0.0370 (15)0.0450 (16)−0.0076 (11)−0.0161 (11)0.0117 (12) C190.0247 (13)0.0316 (14)0.0442 (16)−0.0055 (11)−0.0232 (12)0.0062 (11) C200.0260 (13)0.0272 (13)0.0311 (13)−0.0010 (10)−0.0163 (11)0.0007 (10) C210.0165 (11)0.0188 (11)0.0300 (12)−0.0003 (9)−0.0097 (9)−0.0012 (9) C220.0162 (11)0.0235 (12)0.0287 (12)0.0022 (9)−0.0095 (9)−0.0034 (9) C230.0129 (11)0.0407 (15)0.0341 (14)−0.0028 (10)−0.0092 (10)−0.0014 (11) C240.0277 (14)0.0476 (18)0.0373 (15)−0.0150 (13)−0.0130 (12)−0.0007 (13) C250.0204 (12)0.0294 (13)0.0271 (13)0.0046 (10)−0.0037 (10)−0.0032 (10) C260.0146 (10)0.0285 (12)0.0242 (12)−0.0004 (9)−0.0037 (9)−0.0021 (9) C270.0305 (14)0.0385 (15)0.0249 (13)0.0033 (12)−0.0046 (11)−0.0073 (11) C280.0381 (16)0.0488 (18)0.0200 (12)−0.0009 (13)−0.0061 (11)0.0009 (11) N70.185 (8)0.191 (9)0.219 (10)−0.045 (7)0.062 (7)−0.061 (7) C310.110 (6)0.216 (9)0.097 (5)0.067 (5)0.046 (4)0.071 (5)C320.142 (9)0.268 (14)0.457 (17)0.053 (9)0.071 (12)0.198 (13)B10.0459 (19)0.0272 (15)0.0255 (15)−0.0008 (14)−0.0120 (13)0.0028 (11) F10.0552 (14)0.0650 (15)0.0721 (16)−0.0250 (12)−0.0073 (12)−0.0162 (12) F20.136 (2)0.0401 (11)0.0522 (13)0.0193 (13)−0.0523 (15)0.0049 (9)F30.0422 (10)0.0499 (11)0.0315 (9)0.0071 (8)−0.0087 (8)0.0014 (8)F40.0626 (12)0.0299 (9)0.0356 (9)−0.0032 (8)−0.0194 (9)−0.0026 (7) C290.0270 (13)0.0358 (14)0.0267 (13)−0.0018 (11)−0.0103 (11)0.0065 (11) N60.0182 (10)0.0277 (11)0.0269 (11)−0.0001 (8)−0.0087 (8)−0.0009 (8) C300.0173 (11)0.0269 (12)0.0212 (11)0.0005 (9)−0.0072 (9)−0.0011 (9) Geometric parameters (Å, º)Cu1—N1 2.018 (2)C14—H14A0.9300Cu1—N4 2.041 (2)C15—H15A0.9300Cu1—N6i 2.108 (2)C16—C21 1.394 (4)Cu1—N3ii 2.155 (2)C16—C17 1.397 (4) N1—C7 1.328 (3)C17—C18 1.383 (4) N1—C1 1.396 (3)C17—H17A0.9300 N2—C7 1.364 (3)C18—C19 1.396 (4) N2—C6 1.386 (3)C18—H18A0.9300 N2—C10 1.474 (3)C19—C20 1.392 (4) N3—C15 1.341 (3)C19—H19A0.9300 N3—C14 1.348 (4)C20—C21 1.390 (3) N3—Cu1iii 2.155 (2)C20—H20A0.9300 N4—C22 1.320 (3)C22—C23 1.487 (3) N4—C16 1.398 (3)C23—C24 1.522 (4) N5—C22 1.368 (3)C23—H23A0.9700 N5—C21 1.386 (3)C23—H23B0.9700 N5—C25 1.458 (3)C24—H24A0.9600 C1—C2 1.393 (3)C24—H24B0.9600 C1—C6 1.402 (3)C24—H24C0.9600 C2—C3 1.380 (4)C25—C26 1.509 (4) C2—H2A0.9300C25—H25A0.9700 C3—C4 1.403 (4)C25—H25B0.9700 C3—H3A0.9300C26—C27 1.387 (4) C4—C5 1.384 (4)C26—C30 1.390 (3) C4—H4A0.9300C27—C28 1.383 (4) C5—C6 1.392 (4)C27—H27A0.9300 C5—H5A0.9300C28—C29 1.374 (4) C7—C8 1.492 (4)C28—H28A0.9300 C8—C9 1.517 (4)N7—C31 1.223 (5) C8—H8A0.9700C31—C32 1.482 (5) C8—H8B0.9700C32—H32A0.9600 C9—H9A0.9600C32—H32B0.9600 C9—H9B0.9600C32—H32C0.9600 C9—H9C0.9600B1—F1 1.375 (4) C10—C11 1.511 (4)B1—F2 1.379 (4) C10—H10A0.9700B1—F4 1.387 (4) C10—H10B0.9700B1—F3 1.394 (4) C11—C12 1.383 (4)C29—N6 1.337 (3) C11—C15 1.398 (3)C29—H29A0.9300 C12—C13 1.390 (4)N6—C30 1.348 (3) C12—H12A0.9300N6—Cu1i 2.108 (2) C13—C14 1.382 (4)C30—H30A0.9300 C13—H13A0.9300N1—Cu1—N4126.94 (9)N3—C15—H15A118.1N1—Cu1—N6i101.41 (8)C11—C15—H15A118.1N4—Cu1—N6i104.97 (9)C21—C16—C17120.2 (2) N1—Cu1—N3ii118.24 (8)C21—C16—N4109.5 (2) N4—Cu1—N3ii99.80 (9)C17—C16—N4130.3 (2) N6i—Cu1—N3ii102.48 (9)C18—C17—C16117.4 (3) C7—N1—C1105.5 (2)C18—C17—H17A121.3C7—N1—Cu1128.08 (17)C16—C17—H17A121.3C1—N1—Cu1124.81 (16)C17—C18—C19121.7 (2) C7—N2—C6107.2 (2)C17—C18—H18A119.2C7—N2—C10128.2 (2)C19—C18—H18A119.2C6—N2—C10124.4 (2)C20—C19—C18121.8 (2) C15—N3—C14117.2 (2)C20—C19—H19A119.1C15—N3—Cu1iii119.66 (18)C18—C19—H19A119.1C14—N3—Cu1iii119.59 (19)C21—C20—C19115.9 (2) C22—N4—C16105.4 (2)C21—C20—H20A122.1C22—N4—Cu1127.69 (17)C19—C20—H20A122.1C16—N4—Cu1126.17 (17)N5—C21—C20131.3 (2) C22—N5—C21107.0 (2)N5—C21—C16105.6 (2) C22—N5—C25128.4 (2)C20—C21—C16123.0 (2) C21—N5—C25124.6 (2)N4—C22—N5112.5 (2) C2—C1—N1130.6 (2)N4—C22—C23123.8 (2) C2—C1—C6120.1 (2)N5—C22—C23123.7 (2) N1—C1—C6109.3 (2)C22—C23—C24111.8 (2) C3—C2—C1117.9 (2)C22—C23—H23A109.3C3—C2—H2A121.0C24—C23—H23A109.3C1—C2—H2A121.0C22—C23—H23B109.3C2—C3—C4121.4 (2)C24—C23—H23B109.3C2—C3—H3A119.3H23A—C23—H23B107.9C4—C3—H3A119.3C23—C24—H24A109.5C5—C4—C3121.6 (2)C23—C24—H24B109.5C5—C4—H4A119.2H24A—C24—H24B109.5C3—C4—H4A119.2C23—C24—H24C109.5C4—C5—C6116.6 (2)H24A—C24—H24C109.5C4—C5—H5A121.7H24B—C24—H24C109.5C6—C5—H5A121.7N5—C25—C26113.4 (2) N2—C6—C5132.0 (2)N5—C25—H25A108.9N2—C6—C1105.6 (2)C26—C25—H25A108.9C5—C6—C1122.4 (2)N5—C25—H25B108.9N1—C7—N2112.4 (2)C26—C25—H25B108.9N1—C7—C8122.6 (2)H25A—C25—H25B107.7N2—C7—C8124.9 (2)C27—C26—C30117.8 (2) C7—C8—C9110.5 (2)C27—C26—C25119.9 (2) C7—C8—H8A109.6C30—C26—C25122.3 (2) C9—C8—H8A109.6C28—C27—C26119.2 (3) C7—C8—H8B109.6C28—C27—H27A120.4C9—C8—H8B109.6C26—C27—H27A120.4H8A—C8—H8B108.1C29—C28—C27119.1 (3) C8—C9—H9A109.5C29—C28—H28A120.4C8—C9—H9B109.5C27—C28—H28A120.4H9A—C9—H9B109.5N7—C31—C32170.4 (9) C8—C9—H9C109.5C31—C32—H32A109.5H9A—C9—H9C109.5C31—C32—H32B109.5H9B—C9—H9C109.5H32A—C32—H32B109.5N2—C10—C11112.0 (2)C31—C32—H32C109.5N2—C10—H10A109.2H32A—C32—H32C109.5C11—C10—H10A109.2H32B—C32—H32C109.5。

掺杂氧化铁纳米晶对重金属离子的晶面依赖选择性吸附研究获进展

的调控或限制作用。基于此研究，未来有望将材料的击穿场强提高１０倍以
－
Ｆｅ２０，是一种自然界丰富和热力学稳定的半导体，在光电化学分解水、锂离
子电池、气体传感和生物科技等方面均展现了良好的应用前景。目前，对一Ｆｅ２Ｏ的研究主要聚焦在一Ｆｅ２Ｏ纳米晶的形貌调控和表面结构修饰上，以期通过暴
ＮＥＷＳ
中科院金属所研制出新型海绵超级吸水又吸油
据报道，近日，中国科学院金属所研究人员利用纳米纤维素和石墨烯的协同
器件结构。该结构将ＳＮＳＰＤ器件置于微纳光纤的倏逝场内，实现纳米线对
微纳光纤中传输的光子吸收。光学计算显示，该类结构有望实现高吸收效率的同时，保持很好地宽谱特性。经过上海微系统所巫博士君杰和浙江大学博士徐颖鑫等近３年实验探索，科研团队研制出微纳光纤耦合ＳＮＳＰＤ器
作用，通过浸涂法获得超双亲聚氨酯海绵。该超双亲海绵对水和油类的接触角为０。，能够在短时间内迅速吸附水和油，这是国际上首次报道通过浸涂法直接获
得超双亲聚氨酯海绵材料。该项成果为制备具有特殊浸润性能的多孔弹性材料
及其复合材料提供了新思路，在催化剂载体和智能高分子复合材料领域有望获
得应用。
近几年来，金属所聚合物复合材料研究组致力于纳米纤维素与石墨烯相互

1,8-萘啶衍生物近年来在生物医药领域的应用探究

1,8-萘啶衍生物近年来在生物医药领域的应用探究罗建松;徐涛;张福叶;迟绍明【摘要】近年来1,8-萘啶衍生物在生物医疗领域的研究应用进展很快.随着大量新型1,8-萘啶化合物不断合成出来,并通过大量实验研究发现这类化合物具备良好的生物活性,与其相关的医药性质得到越来越多的开发与研究,在多种疾病治疗领域得到应用:可应用于抗菌,癌症治疗,消炎药等,同时1,8-萘啶类化合物还可用于治疗精神类疾病,如抗抑郁.1,8-萘啶化合物拥有广泛的生物医疗应用前景,随着更多新型1,8-萘啶衍生物不断合成,这类化合物的医药用途也将得到更加深入的研究和应用.【期刊名称】《云南民族大学学报（自然科学版）》【年(卷),期】2018(027)006【总页数】5页(P460-463,478)【关键词】1,8-萘啶化合物;生物医药;有机合成【作者】罗建松;徐涛;张福叶;迟绍明【作者单位】云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500【正文语种】中文【中图分类】O06-1萘啶化合物是一类重要的天然产物和药物结构单元，本身具有多种重要的生物学特性.其中1,8-萘啶衍生物以其与过渡金属配合物优良的光学结构性质及光稳定性，广泛用于特定金属离子和阴离子识别、荧光化学探针、化学传感器、发光材料、超分子、DNA及RNA识别与监测、细胞内特定离子及生物分子的识别、光物理研究领域、生物体免疫系统调节等等[1-7].近年来，随着新型1,8-萘啶衍生物的合成和深入研究，大大拓展了其应用范围，例如光化学治疗，生物活性材料，潜在的太阳能转换材料，人工光合作用等多领域的应用[8-10].同时1,8-萘啶衍生物具有广泛的生物医药用途，例如抗肿瘤、抗抑郁和抗焦虑、抗过敏、抗菌药、抗增殖、抗疟疾、可用作消炎药和止痛剂以及治疗高血压等等[11-15].随着不断对新衍生物的合成和探究，在治疗艾滋病(HIV)方面，1,8-萘啶衍生物也开始展现出优良的治疗能力.萘啶类化合物具有良好的开发应用前景，倍受相关科研工作者的关注.本文将介绍近几年来1,8-萘啶衍生物在生物医学方面的研究应用进展.1 近年来1,8-萘啶化合物的生物活性探究1.1 抗菌活性2016年，Chennam Kishan Prasad团队设计合成了3种新型1,8-萘啶的金属Cu、Co、Zn配合物[16]，并研究了这3种配合物的抗菌活性.该团队培养了4种细菌病原体(金黄色葡萄球菌，枯草芽孢杆菌，大肠杆菌和肺炎克雷伯菌)，在这4种菌株中分别加入相应的1,8-萘啶金属配合物，探究其对这4种细菌病原体的抑制作用，并将结果与相同浓度的标准抗菌药物氨苄青霉素进行比较，发现其中的1,8-萘啶金属Cu配合物(图1化合物1a)具有优秀的抗菌活性.SAKRAM B等采用无溶剂固相研磨反应的方法，合成了一系列新型1,8-萘啶化合物[17]，使用氨苄青霉素作为参考药物，在革兰氏阳性菌金黄色葡萄球菌和革兰氏阴性菌大肠杆菌菌株中对所有合成的产品进行了抗菌活性测试.并以灰黄霉素作为参考药物，在黑曲霉和假丝酵母菌株中测试化合物的抗真菌活性.其中2种化合物(图1化合物1b,1c)表现出很高的抗菌和抗真菌活性.1.2 癌症治疗Behalo Mohamed S等以2-氨基-6-(2-苯氧硫杂环己烷)-4-(2-噻吩)烟腈为起始原料合成的一系列1,8-萘啶衍生物[18]显示出了对乳腺癌和前列腺癌细胞良好的细胞毒性，尤其对前列腺癌细胞展现出非常显著的毒性作用.其中3种化合物(图2化合物2a，2b，2c)对前列腺癌细胞表现出最显著的细胞毒性作用，是潜在的前列腺癌治疗药物.据世卫组织统计，世界上所有死于癌症的人中，占比最大的为肺癌，平均每年约有156万人死于肺癌.化疗被认为是延缓肿瘤生长的主要治疗方法之一，然而化疗治疗癌症在杀伤肿瘤细胞的同时，也可能将正常细胞和免疫细胞一同杀灭，所以化疗是一种“两害相权取其轻”的治疗手段.因此，针对癌症的有效治疗药物有非常高的研发价值.THILAGAM S等合成了一系列基于1,8-萘啶化合物[19]，并测试了这系列化合物对人类癌症细胞的抑制作用.其中发现化合物2d(图2化合物2d)对A549系肺癌细胞具有很好的抑制活性.1.3 抗艾滋病病毒(HIV)活性探究早在2010年Massari Serena团队探究了在1,8-萘啶环C-7位碳原子上接入1-(1,3-苯并噻唑-2-)哌嗪基团(图3化合物3a)[20]，可在被感染的细胞中选择性识别和抑制HIV-1病毒的Tat介导转录蛋白酶，从而抑制HIV-1型病毒复制转录.众所周知，HIV-1是一种逆转录病毒，属于RNA病毒中的一种.逆转录病毒在其生命周期内需要完成将病毒遗传信息整合进宿主细胞核的行动.逆转录病毒自身的整合酶(Integrase)是帮助逆转录病毒把携带病毒遗传信息整合到宿主的DNA的酶.因此整合酶可以作为对抗HIV-1病毒的靶标.目前有3种经美国食品药品监督管理局(FDA)批准用于治疗艾滋病的HIV-1整合酶(IN)链转移抑制剂(INSTIs).基于此，Zhao[21]和Nagasawa[22]等设计合成了一系列新型1,8-萘啶化合物，并测定了这些化合物对HIV-1型病毒整合酶的抑制效果，发现化合物3b(结构见图3)的整体抑制效果最好.该团队还将继续设计合成出更多新型1,8-萘啶化合物并探究对HIV-1型病毒整合酶的抑制效果.1.4 抗抑郁治疗抑郁症是全球一种常见病，据世界卫生组织(WHO)估计共有3.5亿名患者.长期的中度或重度抑郁症可能成为一个严重的疾患.最严重时，抑郁症可引致自杀.每年自杀死亡人数估计高达100万人.WHO预测，到2020年，抑郁症将是全球过早死亡或残疾的第二大原因.根据《精神疾病诊断与统计手册》(DSM-IV)特征，抑郁症的症状表现在正常日常活动和悲伤感中丧失兴趣或乐趣.其他的症状包括内疚感或自卑感，睡眠不足或食欲不振，无精打采.甚至，抑郁症可导致自杀.抑郁症患者自杀率高达3.4%.虽然有许多临床上有用的抗抑郁药物可用，但疾病的流行仍然存在.这可能是由于目前可用的药物功效不足，缺乏对抑郁症病因和病理机制的清晰认识.DharArghya K团队分别在2014年和2015年设计合成了一系列1,8-萘啶衍生物[23-24]，并测试了这些化合物的抗抑郁效果.其中的3种化合物(图4化合物4a，4b，4c)在小鼠实验中取得了不错的抗抑郁效果.该团队将在相关课题中进行更深入的研究.1.5 消炎药DI BRACCIO M等设计合成的一系列新型1,8-萘啶化合物[25]，并测定发现这些化合物均具备良好的抗炎活性，其中化合物5a(结构见图5)在大鼠体内表现出良好的抗炎性质，是潜在的抗炎药物.该团队在小鼠止痛测试中还发现，化合物5a还表现出良好的止痛作用，是有效的消炎和止痛效果的药物.2 小结1,8-萘啶类化合物拥有广泛的生物活性，目前已经在多种疾病治疗中表现出了较为出色的治疗效果.随着新型的1,8-萘啶衍生物不断合成出来，这类化合物的生物医药活性具有巨大潜在的探究价值.同时伴随有机合成技术的发展，必将出现更有针对性、治疗效果更佳、副作用更低的1,8-萘啶有机化合物，作为有机合成的热点并将在生物医药领域继续得到广泛研究.参考文献:【相关文献】[1] HUANG M, LOU Z, PENG X, et al. Synthesis, special secognition to Cu2+ and Cr3+ of the ferrocenyl derivatives[J]. Chinese Journal of Organic Chemistry, 2015, 35(9): 1966-1974.[2] SHIBATA T, NAKATANI K. Fluorescence probe for detecting CCG trinucleotide repeat DNA expansion and slip-out[J]. ChemBioChem: A European Journal of Chemical Biology, 2016, 17(18): 1685-1688.[3] BAIG M Z K, PAWAR S, TULICHALA R P, et al. A single fluorescent probe as systematic sensor for multiple metal ions: Focus on detection and bio-imaging of Pd2+[J]. Sensors and Actuators B: Chemical, 2017, 243: 226-233.[4] SETH S K, DAS N K, AICH K, et al. Exploring contribution of intermolecular interactions in supramolecular layered assembly of naphthyridine co-crystals: insights from hirshfeld surface analysis of their crystalline states[J]. Journal of Molecular Structure, 2013, 1048: 157-165.[5] ZHANG D Y, NIE Y, SANG H, et al. Three structurally related Copper complexes with two isomers: DNA/BSA binding ability, DNA cleavage activity and excellent cytotoxicity[J]. Inorganica Chimica Acta, 2017, 457: 7-18.[6] CHE C M, WAN C W, HO K Y, et al. Strongly luminescent metal-organic compounds: spectroscopic properties and crystal structure of substituted 1,8-naphthyridine and its zinc(Ⅱ) complex[J]. New Journal of Chemistry, 2001, 25(1): 63-65.[7] MALFITANO A M, LAEZZA C, SACCOMANNI G, et al. Immune-modulation andproperties of absorption and blood brain barrier permeability of 1, 8-naphthyridine derivatives[J]. Journal of Neuroimmune Pharmacology, 2013, 8(5): 1077-1086.[8] WHITE T A, DUNBAR K R, THUMMEL R P, et al. Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2(Ⅱ,Ⅱ) dimers[J]. Polyhedron, 2016, 103, Part A: 172-177.[9] MA W, CHEN F, LIU Y, et al. Ruthenium-catalyzed enantioselective hydrogenation of 1, 8-naphthyridine derivatives[J]. Organic letters, 2016, 18(11): 2730-2733.[10] TAMASHIRO B T, CEDANO M R, PHAM A T, et al. Use of a wedge scheme to describe intermolecular proton-coupled electron transfer through the H-bond complex formed between a phenylenediamine-based urea and 1, 8-naphthyridine[J]. The Journal of Physical Chemistry C, 2015, 119(23): 12865-12874.[11] 黄振桂, 林克江, 尹鸿萍, 等. 具有全新机理的DNA旋转酶抑制剂的筛选及抑菌活性[J]. 高等学校化学学报, 2013, 34(8): 1887-1893.[12] PARK T, MAYER M F, NAKASHIMA S, et al. Preparation of 2, 7-diamino-1, 8-naphthyridine: A useful building block for supramolecular chemistry[J]. Synlett, 2005,25(9): 1435-1436.[13] EL-HADIDY S A, SELIM Y A. New synthetic approaches for cytotoxic activity of novel 1, 8-naphthyridine derivatives[J]. Journal of Heterocyclic Chemistry, 2018, 55(1): 103-114. [14] ROMA G, DI BRACCIO M, GROSSI G, et al. 1,8-Naphthyridines Ⅷ. Novel 5-aminoimidazo[1,2-a] [1,8]naphthyridine-6-carboxamide and 5-amino[1,2,4]triazolo[4,3-a] [1,8]naphthyridine-6-carboxamide derivatives showing potent analgesic or anti-inflammatory activity, respectively, and completely devoid of acute gastrolesivity[J]. European Journal of Medicinal Chemistry, 2010, 45(1): 352-366.[15] BHATT S, BAGAL S, BUTOLA S, et al. Antidepressant-and anxiolytic-like effect of novel 5-hydroxytryptamine3 receptor antagonist 2-[4-(3-chlorophenyl) piperazin-1-yl]-1,8-naphthyridine-3-carboxylic acid (7e)-: An approach using rodent behavioral antidepressant and anxiolytic test battery[J]. International Journal of Nutrition, Pharmacology, Neurological Diseases, 2016, 6(2): 81-89.[16] CHENNAM K P, RAVI M, USHAIAH B, et al. Synthesis, characterization, DNA interactions, DNA cleavage, radical scavenging activity, antibacterial, anti-proliferative and docking studies of new transition metal complexes[J]. Journal of Fluorescence, 2016, 26(1): 189-205.[17] SAKRAM B, SONYANAIK B, ASHOK K, et al. Eco-friendly synthesis of 1, 8-naphthyridine 5-aryl-1, 3, 4-oxadiazole derivatives under solvent-free solid-state conditions and their antimicrobial activity[J]. Research on Chemical Intermediates, 2017, 43(3): 1881-1892.[18] BEHALO M S, MELE G. Synthesis and evaluation of pyrido[2,3-d]pyrimidine and 1,8-naphthyridine derivatives as potential antitumor agents[J]. Journal of Heterocyclic Chemistry, 2017, 54(1): 295-300.[19] THILAGAM S, RAJENDRAN S P. Molecular docking and cytotoxic activity of 1, 8-naphthyridine derivatives in human lung cancer[J]. PARIPEX-Indian Journal of Research, 2015, 4(5): 437-439.[20] MASSARI S, DAELEMANS D, BARRECA M L, et al. A 1, 8-naphthyridone derivative targets the HIV-1 Tat-mediated transcription and potently inhibits the HIV-1 replication[J]. Journal of medicinal chemistry, 2009, 53(2): 641-648.[21] ZHAO X Z, SMITH S J, MÉTIFIOT M, et al. 4-Amino-1-hydroxy-2-oxo-1,8-naphthyridine-containing compounds having high potency against raltegravir-resistant integrase mutants of HIV-1[J]. Journal of Medicinal Chemistry, 2014, 57(12): 5190-5202. [22] NAGASAWA J Y, SONG J, CHEN H, et al. 6-Benzylamino 4-oxo-1, 4-dihydro-1, 8-naphthyridines and 4-oxo-1, 4-dihydroquinolines as HIV integrase inhibitors[J]. Bioorganic & medicinal chemistry letters, 2011, 21(2): 760-763.[23] DHAR A K, MAHESH R, JINDAL A, et al. Piperazine analogs of naphthyridine-3-carboxamides and indole-2-carboxamides: novel 5-HT3 receptor antagonists with antidepressant-like activity[J]. Archiv der Pharmazie, 2015, 348(1): 34-45.[24] DHAR A K, MAHESH R, JINDAL A, et al. Design, synthesis, and pharmacological evaluation of novel 2-(4-substituted piperazin-1-yl) 1, 8 naphthyridine 3-carboxylic acids as 5-HT3 receptor antagonists for the management of depression[J]. 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基于贵金属纳米结构的电化学葡萄糖生物传感研究

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钙钛矿催化剂英语

钙钛矿催化剂英语Perovskite Catalysts: A Promising Pathway to a Sustainable FuturePerovskite materials have emerged as a remarkable class of catalysts, offering a versatile and efficient solution to a wide range of environmental and energy-related challenges. These materials, with their unique crystal structure and tunable properties, have captured the attention of researchers worldwide, paving the way for innovative applications in various fields including renewable energy, pollution control, and chemical synthesis.At the heart of perovskite catalysts lies their exceptional ability to facilitate critical chemical reactions. The perovskite structure, consisting of a central metal cation surrounded by an octahedron of anions, provides a highly customizable platform for tailoring catalytic performance. By substituting different elements into the perovskite lattice, researchers can fine-tune the material's electronic structure, surface properties, and catalytic activity, enabling targeted optimization for specific applications.One of the most promising applications of perovskite catalysts is in the realm of renewable energy. Perovskite materials havedemonstrated exceptional efficiency in the water-splitting reaction, a crucial process for the generation of clean hydrogen fuel. By leveraging the unique redox properties of perovskites, researchers have developed highly active and stable catalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), the two half-reactions that comprise water splitting. These perovskite-based catalysts have shown superior performance compared to traditional precious metal-based catalysts, making them a cost-effective and sustainable alternative for large-scale hydrogen production.Moreover, perovskite catalysts have also found applications in the field of carbon dioxide (CO2) reduction, a vital process for mitigating greenhouse gas emissions and achieving a circular carbon economy. Perovskite-based electrocatalysts have demonstrated the ability to selectively convert CO2 into valuable chemicals and fuels, such as carbon monoxide, formic acid, and methanol, with high efficiency and selectivity. This capability holds immense promise for the development of integrated CO2 capture and utilization systems, contributing to a more sustainable and environmentally-friendly future.Beyond renewable energy applications, perovskite catalysts have also made significant strides in the field of pollution control. These materials have shown remarkable catalytic activity in the removal ofvarious air and water pollutants, including nitrogen oxides (NOx), sulfur oxides (SOx), volatile organic compounds (VOCs), and heavy metals. Perovskite-based catalysts can effectively oxidize or reduce these harmful substances, transforming them into less toxic or even benign compounds. This versatility makes perovskite catalysts a promising solution for addressing pressing environmental challenges, such as urban air pollution and water contamination.In the realm of chemical synthesis, perovskite catalysts have also showcased their potential. These materials have been employed in a wide range of organic transformations, including hydrogenation, oxidation, and coupling reactions. Perovskite catalysts have demonstrated superior activity, selectivity, and stability compared to traditional metal-based catalysts, opening up new avenues for the development of more efficient and sustainable chemical processes.The remarkable performance of perovskite catalysts can be attributed to their unique structural and electronic properties. The flexibility of the perovskite structure allows for the incorporation of a diverse range of elements, enabling the fine-tuning of catalytic activity and selectivity. Additionally, the strong metal-oxygen bonds in perovskites confer excellent thermal and chemical stability, crucial for maintaining catalytic performance under harsh reaction conditions.Furthermore, the scalable and cost-effective synthesis methods for perovskite materials have made them increasingly attractive for industrial applications. Compared to traditional precious metal-based catalysts, perovskite catalysts can be produced using more abundant and less expensive raw materials, making them a more economically viable option for large-scale deployment.As the field of perovskite catalysts continues to evolve, researchers are exploring innovative strategies to further enhance their performance and broaden their applications. This includes the development of nanostructured perovskite catalysts with increased surface area and active site density, the integration of perovskites with other functional materials to create hybrid catalytic systems, and the exploration of novel perovskite compositions for targeted catalytic reactions.In conclusion, perovskite catalysts have emerged as a transformative technology, offering a promising pathway towards a more sustainable future. Their versatility, efficiency, and cost-effectiveness have positioned them as a game-changing solution in renewable energy, pollution control, and chemical synthesis. As research and development in this field continue to advance, the impact of perovskite catalysts is poised to extend far beyond their current applications, contributing to a cleaner, more environmentally-friendly, and resource-efficient world.。

1,2,4,5-苯四甲酸Zn(Ⅱ)配合物的合成、晶体结构及热稳定性

1,2,4,5-苯四甲酸Zn(Ⅱ)配合物的合成、晶体结构及热稳定性石显璘;郑长征;薛凝;杨森;武耀博【摘要】以1,2,4,5-苯四甲酸(H4 BTA)为主要配体,加入辅配4,4 '联吡啶(bipy)和金属盐Zn(NO3)2·6H2O,通过水热法合成出一个Zn(Ⅱ)的配合物晶体[Zn(H2 BTA) (bipy)(H2 O)]n.通过元素分析、红外光谱、X-射线单晶洐射、热重分析和X-射线粉末衍射等手段对此配合物的特性进行表征.X-射线单晶衍射结果表明,此配合物属于单斜晶系,P21/n空间群,晶胞参数为a=0.948 9(3)nm,b=0.7274(2)nm,c=1.625 2(4)nm,α=90.00°,β=95.22(4)°,γ=90.00°,V=1.11711(50)nm3,Z=4;热重分析结果表明其具有较好的稳定性;X-射线粉末洐射分析结果表明其具有较高纯度.【期刊名称】《纺织高校基础科学学报》【年(卷),期】2015(028)003【总页数】5页(P348-352)【关键词】1,2,4,5-苯四甲酸;4,4 '-联吡啶;晶体结构;锌配合物;热稳定性【作者】石显璘;郑长征;薛凝;杨森;武耀博【作者单位】西安工程大学环境与化学工程学院,陕西西安710048;西安工程大学环境与化学工程学院,陕西西安710048;西安工程大学环境与化学工程学院,陕西西安710048;西安工程大学环境与化学工程学院,陕西西安710048;西安工程大学环境与化学工程学院,陕西西安710048【正文语种】中文【中图分类】O626羧酸配体在合成金属-有机配位聚合物的众多配体中具有重要地位.由于羧酸配体骨架较稳定,羧基的配位能力强,且羧基的配位模式灵活多变,因此其在金属-有机配位聚合物的合成中得到了广泛应用[1-7].以羧酸类配体为原料设计合成的配位聚合物结构新颖多样，在光学、气体储存、催化和磁性材料等领域具有广阔的发展前景和应用价值，深受广大学者的重视.1,2,4,5-苯四甲酸具有很好的对称性,在一定的条件下,苯环上的四个羧酸可以部分或者全部去质子化参与配位.另外,质子化的羧基还可以作为氢键的给体和受体[8-9],因此其是构筑金属有机骨架配合物的理想材料[10-11].辅助配体的添加对配合物的构筑也有很大的影响,最常见的如桥连的含氮配体[12],4,4′-联吡啶.4,4′-联吡啶是直线型分子,它可作为桥连配体通过两个吡啶环上的氮原子与中心金属离子配位.含氮配体类配位模式稳定,常以端基的形式起配位作用，与其他配体如羧酸类配体等形成混和配体配位,构筑出许多结构新颖的配位聚合物[13-15].因此,本文以1,2,4,5-苯四甲酸(H4BTA)为主要配体,加入辅配4,4′-联吡啶(bipy)和金属盐Zn(NO3)2·6H2O合成出一个Zn(Ⅱ)的配合物晶体[Zn(H2BTA)(bipy)(H2O)]n.1.1 仪器与试剂(1) 仪器 Bruker Smart-APEXIIXCCD射线单晶衍射仪(德国Bruker公司)，Vario EL Ⅲ元素分析仪(德国Elementar 公司)，FT IR-8400红外光谱仪(日本岛津公司)，TGA/S DTA851e热重分析仪(瑞士METTLER公司)，D/Max-3c全自动X射线衍射仪(日本Rigalcu公司)，DGG-9070BD自动程控烘箱(杭州卓驰仪器有限公司)，CP114电子天平(上海奥豪斯仪器有限公司)，水热反应釜(济南恒化科技有限公司).(2 )试剂 1,2,4,5-苯四甲酸、4,4′-联吡啶(梯希爱上海化成工业发展有限公司)、N,N-二甲基甲酰胺、硝酸锌(天津市福晨化学试剂厂)、二次蒸馏水.1.2 配合物的合成及晶体的培养将0.1mmol 的Zn(NO3)2·6H2O(29.7mg)、0.1mmol H4BTA配体(25.4mg)、0.1mmol辅配bipy (15.6mg)、1mL DMF和9mL二次蒸馏水封入25mL带聚四氟乙烯内衬的不锈钢水热反应釜内,在100℃下晶化72h,然后以3℃·h-1 的控温速率降至室温,得到白色透明晶体,用DMF将晶体充分洗涤并低温烘干．元素分析结果(%)显示实测值(计算值)为C,39.73(39.80);H, 1.24(1.99);N,4.62(4.64).1.3 晶体结构的测定选取大小合适、几何形状规则、光滑而透明的配合物晶体置于Bruker Smart-APEX Ⅱ CCD单晶衍射仪上,在温度296(2) K下,用经石墨单色器单色化的MoKα射线(λ=0.071 073nm),以φ-ω 扫描方式收集晶体的衍射数据,对全部衍射数据进行经验吸收校正及Lp校正. 晶体结构通过SHELXL-97软件由直接法解出[16].采用理论加氢的方法确定氢原子,对氢原子和非氢原子分别采用各向同性和各向异性热参数,进行全矩阵最小二乘法修正[17].晶体结构解析和精修均由SHELXL-97完成.配合物的晶体学数据及结构精修参数均列于表1.2.1 红外光谱分析采用KBr压片法测定配体(H4BTA)及Zn(Ⅱ)配合物在波数为4 000～500cm-1范围内的红外光谱(图1)。

有机化学常用网址整理

有机化学常用网址整理http://www.chem.ucalgary.ca/courses/351/Carey5th/Carey.html/iupac/nomenclature/On-Line Learning Center"Organic Chemistry" 5th ed. by Francis A. CareyIUPAC Nomenclature of Organic Chemistry有机合成：Organic Syntheses(有机合成手册), John Wiley & Sons (免费)/Named Organic Reactions Collection from the University ofOxford (有机合成中的命名反应库) (免费)/thirdyearcomputing/NamedOrganicReac...有机化学资源导航Organic Chemistry Resources Worldwide/有机合成文献综述数据库Synthesis Reviews (免费)/srev/srev.htmCAMEO (预测有机化学反应产物的软件)/products/cameo/index.shtmlCarbohydrate Letters (免费,摘要)/Carbohydrate_Letters/Carbohydrate Research (免费,摘要)/locate/carresCurrent Organic Chemistry (免费,摘要)/coc/index.htmlElectronic Encyclopedia of Reagents for Organic Synthesis (有机合成试剂百科全书e-EROS)/eros/European Journal of Organic Chemistry (免费,摘要)/jpages/1434-193X/Methods in Organic Synthesis (MOS,有机合成方法)/is/database/mosabou.htmOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlRussian Journal of Bioorganic Chemistry (Bioorganicheskaya Khimiya) (免费,摘要) http://www.wkap.nl/journalhome.htm/1068-1620Russian Journal of Organic Chemistry (Zhurnal Organicheskoi Khimii) (免费,摘要) http://www.maik.rssi.ru/journals/orgchem.htmScience of Synthesis: Houben-Weyl Methods of Molecular Transformation/Solid-Phase Synthesis database (固相有机合成)/chem_db/sps.htmlSynthetic Communications (免费,摘要)/servlet/product/productid/SCCSyntheticPages (合成化学数据库) (免费)/The Complex Carbohydrate Research Center (复杂碳水化合物研究中心)/合成材料老化与应用(免费,目录)/default.html金属卡宾络合物催化的烯烃复分解反应(免费)/html/books/O61BG/b1/2002/2.6%20.htm上海化学试剂研究所/英国化学数据服务中心CDS (Chemical Database Service)/cds/cds.html英国皇家化学会碳水化合物研究组织(Carbohydrate Group of the Royal Society of Chemistry)/lap/rsccom/dab/perk002.htm有机反应催化学会(ORCS, Organic Reaction Catalysis Society)/有机合成练习(免费)/中国科学院成都有机化学研究所：催化与环境工程研究发展中心/MainIndex.htm金属有机及元素有机化学：CASREACT - Chemical Reactions Database(CAS的化学反应数据库)/CASFILES/casreact.html日本丰桥大学Jinno实验室的研究数据库(液相色谱、多环芳烃/药物/杀虫剂的紫外谱、物性) (免费)http://chrom.tutms.tut.ac.jp/JINNO/ENGLISH/RESEARCH/research...A New Framework for Porous Chemistry (金属有机骨架) (免费)/alchem/articles/1056983432324.htmlActa Crystallographica Section B (免费,摘要)/b/journalhomepage.htmlActa Crystallographica Section E (免费,摘要)/e/journalhomepage.htmlBibliographic Notebooks for Organometallic Chemistryhttp://www.ensc-lille.fr/recherche/cbco/bnoc.htmlBiological Trace Element Research (生物痕量元素研究杂志) (免费,摘要)/JournalDetail.pasp?issn=0163-4984...Journal of Organometallic Chemistry (免费,摘要)/locate/jnlabr/jomOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlSyntheticPages (合成化学数据库) (免费)/金属卡宾络合物催化的烯烃复分解反应(免费)/html/books/O61BG/b1/2002/2.6%20.htm金属有机参考读物：The Organometallic HyperTextBook by Rob Toreki/organomet/index.html金属有机化学国家重点实验室，中国科学院上海有机所/元素有机化学国家重点实验室（南开大学）/在线网络课程：有机金属反应和均相催化机理(Dermot O'Hare 主讲)/icl/dermot/organomet/药物化学：Fisher Scientific/PubMed: MEDLINE和PREMEDLINE (免费)/PubMed/生物医药:BioMedNet: The World Wide Club for the Biological and Medical Community/AIDSDRUGS (艾滋病药物) (免费)/pubs/factsheets/aidsinfs.htmlautodock (分子对接软件) (免费)/pub/olson-web/doc/autodock/DIRLINE (卫生与生物医药信息源库) (免费)/HISTLINE (医药史库) (免费)/TOXNET (化合物毒性相关数据库系列) (免费)/日本药典，第14版(免费)http://jpdb.nihs.go.jp/jp14e/index.html小分子生物活性数据库ChemBank (免费)/Ashley Abstracts Database (药物研发、市场文献摘要) (免费)/databases/ashley/search.aspBIOSIS/BIOSIS/ONLINE/DBSS/biosisss.html从检索药物交易信息库PharmaDeals (部分免费)/从ChemWeb检索有机药物用途及别名库Negwer: organic-chemical drugs and their synonyms (部分免费)/negwer/negwersearch.html美国常用药品索引库RxList (免费)/美国国家医学图书馆NLM的免费在线数据库(免费)/hotartcl/chemtech/99/tour/internet.html制药公司目录(Pharmaceutical Companies on Virtual Library: Pharmacy Page) /company.html37℃医学网/AAPS PharmSci (免费,全文)/Abcam Ltd.有关抗体、试剂的销售，抗体的搜索)/Acta Pharmaceutica (免费,摘要)http://public.srce.hr/acphee/Advanced Drug Delivery Reviews (免费,摘要)http://www.elsevier.nl/locate/drugdelivAmerican Journal of Drug and Alcohol Abuse (免费,摘要)/servlet/product/productid/ADAAmerican Journal of Pharmaceutical Education (AJPE) (免费,全文)/Amgen Inc. (医药)/Anita's web picks (药学与药物化学信息导航)http://wwwcmc.pharm.uu.nl/oyen/webpicks.htmlAnnals of Clinical Microbiology and Antimicrobials (免费,全文)/Annual Review of Pharmacology and Toxicology (免费,摘要)/Anti-Cancer Drug Design (免费,摘要)/antcan/学习有机化学必须知道的关于国内外有机文献杂志的数据库网址及杂志名称ScienceDirect (SD)网址：/(1) Catalysis Communications （催化通讯）(2) Journal of Molecular Catalysis A: Chemical （分子催化A：化学）(3) Tetrahedron (T) （四面体）(4) Tetrahedron: Asymmetry (TA) （四面体：不对称）(5) Tetrahedron Letters (TL) （四面体快报）(6) Applied Catalysis A: General （应用催化A）2． EBSCOhost数据库网址：/(1) Synthetic Communcations （合成通讯）(2) Letters in Organic Chemistry (LOC)(3) Current Organic Synthesis(4) Current Organic Chemistry3. Springer数据库网址：http:// /(1) Molecules （分子）(2) Monatshefte für Chemie / Chemical Monthly （化学月报）(3) Science in China Series B: Chemistry （中国科学B）(4) Catalysis Letts （催化快报）4. ACS Publications (美国化学会)网址：/(1) Journal of the American Chemical Society (JACS) （美国化学会志）(2) Organic Letters (OL) （有机快报）(3) The Journal of Organic Chemistry (JOC) （美国有机化学）(4) Journal of Medicinal Chemistry (JMC) （美国药物化学）(5) Chemical Reiew （化学评论）5. Royal Society of Chemistry (RSC) (英国皇家化学会)网址：/Publishing/Journals/Index.asp(1) Green Chemistry （绿色化学）(2) Chemical Communications (CC) （化学通讯）(3) Chemical Society Reviews （化学会评论）(4) Journal of the Chemical Society （化学会志）Journal of the Chemical Society, Perkin Transactions 1 (1972-2002)Journal of the Chemical Society, Perkin Transactions 2 (1972-2002)Journal of the Chemical Society B: Physical Organic (1966-1971)Journal of the Chemical Society C: Organic (1966-1971)(5) Organic & Biomolecular Chemistry (OBC) （有机生物化学）/publishing/jo ... p?type=CurrentIssue6. Wiley网址：/(1) Advanced Synthesis & Catalysis (ASC) （先进合成催化）(2) Angewandte Chemie International Edition （德国应用化学）(3) Chemistry - A European Journal （欧洲化学）(4) Chinese Journal of Chemistry （中国化学）(5) European Journal of Organic Chemistry （欧洲有机化学）(6) Helvetica Chimica Acta （瑞士化学）(7) Heteroatom Chemistry （杂原子化学）7. Ingent网址：/(1) Journal of Chemical Research (JCR) （化学研究杂志）(2) Canadian Journal of Chemistry （加拿大化学）(3) Current Organic Chemistry(4) Mini-Reviews in Organic Chemistry(5) Phosphorus, Sulfur, and Silicon and the Related Elements （磷、硫、硅和相关元素）(6) Letters in Organic Chemistry8. Taylor & Francis数据库网址：http://www.journalsonline.tandf. ... sp?referrer=default(1) Synthetic Communications(2) Journal of Sulfur Chemistry（硫化学杂志）(3) Phosphorus, Sulfur, and Silicon and the Related Elements9. Thieme数据库网址：/(1) Synlett （合成快报）(2) Synthesis （合成）10. 日本化学会网址：(1) Chem. Lett. (CL) （化学快报）http://www.jstage.jst.go.jp/browse/cl/_vols(2) Bull. Chem. Soc. Jpn. http://www.csj.jp/journals/bcsj/index.html11. 澳大利亚化学会（Australian Journal of Chemistry）http://www.publish.csiro.au/nid/52.htm12．巴西化学会.br/13．Molecules/molecules/14．韩国化学会http://journal.kcsnet.or.kr/15．印度化学会http://www.niscair.res.in/Scienc ... hin.htm&d=test816．国际有机制备和程序（Organic Preparations and Procedures International，OPPI）/17．有机化学/index.htm有机合成：Organic Syntheses(有机合成手册), John Wiley & Sons (免费)/Named Organic Reactions Collection from the University ofOxford (有机合成中的命名反应库) (免费)/thirdyearcomputing/NamedOrganicReac...有机化学资源导航Organic Chemistry Resources Worldwide/有机合成文献综述数据库Synthesis Reviews (免费)/srev/srev.htmCAMEO (预测有机化学反应产物的软件)/products/cameo/index.shtmlCarbohydrate Letters (免费,摘要)/Carbohydrate_Letters/Carbohydrate Research (免费,摘要)/locate/carresCurrent Organic Chemistry (免费,摘要)/coc/index.htmlElectronic Encyclopedia of Reagents for Organic Synthesis (有机合成试剂百科全书e-EROS)/eros/European Journal of Organic Chemistry (免费,摘要)/jpages/1434-193X/Methods in Organic Synthesis (MOS,有机合成方法)/is/database/mosabou.htmOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlRussian Journal of Bioorganic Chemistry (Bioorganicheskaya Khimiya) (免费,摘要) http://www.wkap.nl/journalhome.htm/1068-1620Russian Journal of Organic Chemistry (Zhurnal Organicheskoi Khimii) (免费,摘要) http://www.maik.rssi.ru/journals/orgchem.htmScience of Synthesis: Houben-Weyl Methods of Molecular Transformation/Solid-Phase Synthesis database (固相有机合成)/chem_db/sps.htmlSynthetic Communications (免费,摘要)/servlet/product/productid/SCCSyntheticPages (合成化学数据库) (免费)/The Complex Carbohydrate Research Center (复杂碳水化合物研究中心)/合成材料老化与应用(免费,目录)/default.html金属卡宾络合物催化的烯烃复分解反应(免费)/html/books/O61BG/b1/2002/2.6%20.htm上海化学试剂研究所/英国化学数据服务中心CDS (Chemical Database Service)/cds/cds.html英国皇家化学会碳水化合物研究组织(Carbohydrate Group of the Royal Society of Chemistry)/lap/rsccom/dab/perk002.htm有机反应催化学会(ORCS, Organic Reaction Catalysis Society)/有机合成练习(免费)/中国科学院成都有机化学研究所：催化与环境工程研究发展中心/MainIndex.htm金属有机及元素有机化学：CASREACT - Chemical Reactions Database(CAS的化学反应数据库)/CASFILES/casreact.html日本丰桥大学Jinno实验室的研究数据库(液相色谱、多环芳烃/药物/杀虫剂的紫外谱、物性) (免费)http://chrom.tutms.tut.ac.jp/JINNO/ENGLISH/RESEARCH/research...A New Framework for Porous Chemistry (金属有机骨架) (免费)/alchem/articles/1056983432324.htmlActa Crystallographica Section B (免费,摘要)/b/journalhomepage.htmlActa Crystallographica Section E (免费,摘要)/e/journalhomepage.htmlBibliographic Notebooks for Organometallic Chemistryhttp://www.ensc-lille.fr/recherche/cbco/bnoc.htmlBiological Trace Element Research (生物痕量元素研究杂志) (免费,摘要)/JournalDetail.pasp?issn=0163-4984...Journal of Organometallic Chemistry (免费,摘要)/locate/jnlabr/jomOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlSyntheticPages (合成化学数据库) (免费)/金属卡宾络合物催化的烯烃复分解反应(免费)/html/books/O61BG/b1/2002/2.6%20.htm金属有机参考读物：The Organometallic HyperTextBook by Rob Toreki/organomet/index.html金属有机化学国家重点实验室，中国科学院上海有机所/元素有机化学国家重点实验室（南开大学）/在线网络课程：有机金属反应和均相催化机理(Dermot O'Hare 主讲)/icl/dermot/organomet/药物化学：Fisher Scientific/PubMed: MEDLINE和PREMEDLINE (免费)/PubMed/生物医药:BioMedNet: The World Wide Club for the Biological and Medical Community/AIDSDRUGS (艾滋病药物) (免费)/pubs/factsheets/aidsinfs.htmlautodock (分子对接软件) (免费)/pub/olson-web/doc/autodock/DIRLINE (卫生与生物医药信息源库) (免费)/HISTLINE (医药史库) (免费)/TOXNET (化合物毒性相关数据库系列) (免费)/日本药典，第14版(免费)http://jpdb.nihs.go.jp/jp14e/index.html小分子生物活性数据库ChemBank (免费)/Ashley Abstracts Database (药物研发、市场文献摘要) (免费)/databases/ashley/search.aspBIOSIS/BIOSIS/ONLINE/DBSS/biosisss.html从检索药物交易信息库PharmaDeals (部分免费)/从ChemWeb检索有机药物用途及别名库Negwer: organic-chemical drugs and their synonyms (部分免费)/negwer/negwersearch.html美国常用药品索引库RxList (免费)/美国国家医学图书馆NLM的免费在线数据库(免费)/hotartcl/chemtech/99/tour/internet.html制药公司目录(Pharmaceutical Companies on Virtual Library: Pharmacy Page) /company.html37℃医学网/AAPS PharmSci (免费,全文)/Abcam Ltd.有关抗体、试剂的销售，抗体的搜索)/Acta Pharmaceutica (免费,摘要)http://public.srce.hr/acphee/Advanced Drug Delivery Reviews (免费,摘要)http://www.elsevier.nl/locate/drugdelivAmerican Journal of Drug and Alcohol Abuse (免费,摘要)/servlet/product/productid/ADAAmerican Journal of Pharmaceutical Education (AJPE) (免费,全文)/Amgen Inc. 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金属有机化学第一章-精品文档

E. O. Fischer
Wilkinson
11. 1971年Monsato把下列反应实现工业化
CH3OH + CO Catalyst [Rh] + ICH3COOH 99%
12. 1982年Bergman等人先后发现饱和CH的活化。
RCH3 + [M]
RCH2-M-H
Crabtree, R. H. J. Organomet. Chem. 2019, 689, 4083-4091
7. 钱长涛，杜灿屏，稀土金属有机化学，化学工业出版社，2019年
American Chemical Society Journals
/journal/
The Royal Society Journals
/ Wiley Journals
www3.interscience.wiley/journal/
7. 1956年，Longuet-Higgins and Orgel 从理论上预测具有反芳香性的环丁二烯配合物的存在，2年后预测被Criegee and Hubel 证实。
M(CO)n
M = Mo, Fe, Co, etc
K. Lammertsma, et al Angew. Chem. Int. Ed. 2009, 48, 3104-3107
三.1. 1827年Zeise Salt K[PtCl3(C2H4)]的发现
H Cl Pt Cl H
H H Cl
-
2.1888年， Mond and Langer:
Ni (inpure) + 4 CO
[Ni(CO)4]
3.1919年，Hein
CrCl3 + PhMgBr
直到X-射线技术的发现和使用才确定其结构

The chemistry and applications of metal organic framworks

DOI: 10.1126/science.1230444, (2013);341 Science et al.Hiroyasu Furukawa The Chemistry and Applications of Metal-Organic FrameworksThis copy is for your personal, non-commercial use only.clicking here.colleagues, clients, or customers by , you can order high-quality copies for your If you wish to distribute this article to othershere.following the guidelines can be obtained by Permission to republish or repurpose articles or portions of articles): May 10, 2014 (this information is current as of The following resources related to this article are available online at/content/341/6149/1230444.full.html version of this article at:including high-resolution figures, can be found in the online Updated information and services, /content/suppl/2013/08/29/341.6149.1230444.DC1.html can be found at:Supporting Online Material /content/341/6149/1230444.full.html#ref-list-1, 13 of which can be accessed free:cites 358 articles This article /content/341/6149/1230444.full.html#related-urls 2 articles hosted by HighWire Press; see:cited by This article has been/cgi/collection/chemistry Chemistrysubject collections:This article appears in the following registered trademark of AAAS.is a Science 2013 by the American Association for the Advancement of Science; all rights reserved. The title Copyright American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the Science o n M a y 10, 2014w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o m/10.1126/science.1230444Cite this article as H. FurukawaScienceDOI: 10.1126/science.1230444 liations is available in the full article online.*Corresponding author. E-mail: yaghi@30 AUGUST 2013 VOL 341 SCIENCE Published by AAASThe Chemistry and Applications of Metal-Organic FrameworksHiroyasu Furukawa,1,2Kyle E.Cordova,1,2Michael O’Keeffe,3,4Omar M.Yaghi1,2,4* Crystalline metal-organic frameworks(MOFs)are formed by reticular synthesis,which creates strong bonds between inorganic and organic units.Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability.These characteristics allow the interior of MOFs to be chemically altered for use in gas separation,gas storage,and catalysis,among other applications.The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids.MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.T he past decade has seen explosive growth in the preparation,characterization,andstudy of materials known as metal-organic frameworks(MOFs).These materials are con-structed by joining metal-containing units[sec-ondary building units(SBUs)]with organic linkers, using strong bonds(reticular synthesis)to create open crystalline frameworks with permanent po-rosity(1).The flexibility with which the metal SBUs and organic linkers can be varied has led to thousands of compounds being prepared and studied each year(Figs.1and2).MOFs have ex-ceptional porosity and a wide range of potential uses including gas storage,separations,and ca-talysis(2).In particular,applications in energy technologies such as fuel cells,supercapacitors, and catalytic conversions have made them ob-jects of extensive study,industrial-scale produc-tion,and application(2–4).Among the many developments made in this field,four were particularly important in advanc-ing the chemistry of MOFs:(i)The geometric principle of construction was realized by the link-ing of SBUs with rigid shapes such as squares and octahedra,rather than the simpler node-and-spacer construction of earlier coordination net-works in which single atoms were linked by ditopic coordinating linkers(1).The SBU approach not only led to the identification of a small number of preferred(“default”)topologies that could be targeted in designed syntheses,but also was cen-tral to the achievement of permanent porosity in MOFs(1).(ii)As a natural outcome of the use of SBUs,a large body of work was subsequently reported on the use of the isoreticular principle (varying the size and nature of a structure without changing its underlying topology)in the design of MOFs with ultrahigh porosity and unusuallylarge pore openings(5).(iii)Postsynthetic mod-ification(PSM)of MOFs—incorporating organicunits and metal-organic complexes through re-actions with linkers—has emerged as a powerfultool for changing the reactivity of the pores(e.g.,creating catalytic sites)(6).(iv)Multivariate MOFs(MTV-MOFs),in which multiple organic function-alities are incorporated within a single framework,have provided many opportunities for designingcomplexity within the pores of MOFs in a con-trolled manner(7).Below,we focus on these aspects of MOFchemistry because they are rarely achieved in oth-er materials and because they lead to the previous-ly elusive synthesis of solids by design.Unlikeother extended solids,MOFs maintain their under-lying structure and crystalline order upon expan-sion of organic linkers and inorganic SBUs,aswell as after chemical functionalization,whichgreatly widens the scope of this chemistry.Wereview key developments in these areas and dis-cuss the impact of this chemistry on applicationssuch as gas adsorption and storage,catalysis,andproton conduction.We also discuss the conceptof MTV-MOFs in relation to the sequence of func-tionality arrangement that is influenced by theelectronic and/or steric interactions among thefunctionalities.Highly functional synthetic crys-talline materials can result from the use of suchtechniques to create heterogeneity within MOFstructures.Design of Ultrahigh PorosityDuring the past century,extensive work was doneon crystalline extended structures in which metalions are joined by organic linkers containing Lewisbase–binding atoms such as nitriles and bipyridines(8,9).Although these are extended crystal struc-tures and not large discrete molecules such as poly-mers,they were dubbed coordination“polymers”—a term that is still in use today,although we preferthe more descriptive term MOFs,introduced in1995(10)and now widely accepted.Becausethese structures were constructed from long or-ganic linkers,they encompassed void space andtherefore were viewed to have the potential to be1Department of Chemistry,University of California,Berkeley,CA94720,USA.2Materials Sciences Division,Lawrence Berkeley National Laboratory,Berkeley,CA94720,USA.3Department of Chemistry,Arizona State University,Tempe,AZ87240,USA. 4NanoCentury KAIST Institute and Graduate School of Energy,Environment,Water,and Sustainability(World Class Univer-sity),Daejeon305-701,Republic of Korea.*Corresponding author.E-mail:yaghi@ln(No.ofstructures)YearDoubling time9.3 years5.7 years3.9 years2010200520001995199019851980197512108642No.ofMOFstructures7000600050004000300020001000Year2122222199199199199199198198198198198197197197197Total (CSD)Extended (1D, 2D, 3D)MOFs (3D)Fig.1.Metal-organic framework structures(1D,2D,and3D)reported in the Cambridge Struc-tural Database(CSD)from1971to2011.The trend shows a striking increase during this period for all structure types.In particular,the doubling time for the number of3D MOFs(inset)is the highest among all reported metal-organic structures. SCIENCE VOL34130AUGUST20131230444-1BAZn 4O(CO 2)6M 3O 3(CO 2)3 (M = Zn, Mg, Co, Ni, Mn, Fe, and Cu)Ni 4(C 3H 3N 2)8In(C 5HO 4N 2)4Zr 6O 4(OH)4-(CO 2)12Zr 6O 8(CO 2)8M 3O(CO 2)6 (M = Zn, Cr, In, and Ga)M 2(CO 2)4(M = Cu, Zn, Fe, Mo, Cr, Co, and Ru)Zn(C 3H 3N 2)4Na(OH)2(SO 3)3Cu 2(CNS)4H 2BDCH 4DOTH 2BDC-X (X = Br, OH, NO 2, and NH 2)H 2BDC-(X)2(X = Me, Cl, COOH, OC 3H 5, and OC 7H 7)H 4ADBFumaric acidOxalic acidH 4ATC H 3THBTSH 3ImDCDTOAADPH 3BTPTIPA Gly-AlaH 4DH9PhDC H 4DH11PhDCH 3BTCIr(H 2DPBPyDC)(PPy)2+H 6BTETCADCDPBN BPP34C10DAH 3BTB (X = CH)H 3TATB (X = N)H 3BTE (X = C ≡C)H 3BBC (X = C 6H 4)H 6TPBTM (X = CONH)H 6BTEI (X = C ≡C)H 6BTPI (X = C 6H 4)H 6BHEI (X = C ≡C−C ≡C)H 6BTTI (X = (C 6H 4)2)H 6PTEI (X = C 6H 4−C ≡C)H 6TTEI (X = C ≡C-C 6H 4-C ≡C)H 6BNETPI (X = C ≡C−C 6H 4−C ≡C−C ≡C)H 6BHEHPI (X = (C 6H 4−C ≡C)2)COOHCOOHCOOHCOOH COOHCOOHOH HOCOOHCOOHXCOOHCOOHX XCOOHHOOCCOOHHOOC OHOO OHNCOOHHOOCNHOOCCOOHN NH HOOCCOOHNNH N HNNHN SO 3H SO 3HHO 3SOHHOOH NH 2H 2NSSN NNN NNNCOOHHOOCCOOHH N H 2NOCOOHOHCOOHHOCOOHOHHOCOOHCOOHHOOCCOOHX XXCOOHHOOCCOOHNN OH OHClClCOOHHOOCCOOHCOOHCOOHHOOCOOOOOCOOHCOOH OOOOONNCOOHCOOHIr NN+COOHHOOCCOOHXXXCOOHCOOHHOOCCOOHHOOCCOOHXXX Al(OH)(CO 2)2 VO(CO 2)2Fig.2.Inorganic secondary building units (A)and organic linkers (B)referred to in the text.Color code:black,C;red,O;green,N;yellow,S;purple,P;light green,Cl;blue polyhedra,metal ions.Hydrogen atoms are omitted for clarity.AIPA,tris(4-(1H -imidazol-1-yl)phenyl)amine;ADP,adipic acid;TTFTB4–,4,4′,4′′,4′′′-([2,2′-bis(1,3-dithiolylidene)]-4,4′,5,5′-tetrayl)tetrabenzoate.30AUGUST 2013VOL 341SCIENCE 1230444-2REVIEWpermanently porous,as is the case for zeolites.The porosity of these compounds was investigated in the1990s by forcing gas molecules into the crev-ices at high pressure(11).However,proof of per-manent porosity requires measurement of reversible gas sorption isotherms at low pressures and tem-peratures.Nonetheless,as we remarked at that time(12),it was then commonplace to refer to materials as“porous”and“open framework”even though such proof was lacking.The first proof of permanent porosity of MOFs was obtained by mea-surement of nitrogen and carbon dioxide isotherms on layered zinc terephthalate MOF(12).A major advance in the chemistry of MOFs came in1999when the synthesis,x-ray single-crystal structure determination,and low-temperature, low-pressure gas sorption properties were reported for the first robust and highly porous MOF,MOF-5 (13).This archetype solid comprises Zn4O(CO2)6 octahedral SBUs each linked by six chelating 1,4-benzenedicarboxylate(BDC2–)units to give a cubic framework(Fig.2,figs.S2and S3,and tables S1and S2).The architectural robustness of MOF-5allowed for gas sorption measurements, which revealed61%porosity and a Brunauer-Emmett-Teller(BET)surface area of2320m2/g (2900m2/g Langmuir).These values are substan-tially higher than those commonly found for zeo-lites and activated carbon(14).To prepare MOFs with even higher surface area(ultrahigh porosity)requires an increase in storage space per weight of the material.Longer organic linkers provide larger storage space and a greater number of adsorption sites within a given material.However,the large space within the crys-tal framework makes it prone to form interpen-etrating structures(two or more frameworks grow and mutually intertwine together).The most effec-tive way to prevent interpenetration is by making MOFs whose topology inhibits interpenetration because it would require the second framework to have a different topology(15).Additionally, it is important to keep the pore diameter in the micropore range(below2nm)by judicious se-lection of organic linkers in order to maximize the BETsurface area of the framework,because it is known that BET surface areas obtained from isotherms are similar to the geometric surface areas derived from the crystal structure(16).In2004, MOF-177[Zn4O(BTB)2;BTB=4,4′,4′′-benzene-1,3,5-triyl-tribenzoate]was reported with the high-est surface area at that time(BET surface area= 3780m2/g,porosity=83%;Figs.3A and4)(15), which satisfies the above requirements.In2010, the surface area was doubled by MOF-200and MOF-210[Zn4O(BBC)2and(Zn4O)3(BTE)4(BPDC)3, respectively;BBC3–=4,4′,4′′-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate;BTE= 4,4′,4′′-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)) tribenzoate;BPDC=biphenyl-4,4′-dicarboxylate] to produce ultrahigh surface areas(4530m2/g and6240m2/g,respectively)and porosities(90% and89%)(17).An x-ray diffraction study performed on a sin-gle crystal of MOF-5dosed with nitrogen or argon gas identified the adsorption sites within the pores(18).The zinc oxide SBU,the faces,and,sur-prisingly,the edges of the BDC2–linker serve asadsorption sites.This study uncovered the originof the high porosity and has enabled the design ofMOFs with even higher porosities(Fig.4and ta-ble S3).Moreover,it has been reported that ex-panded tritopic linkers based on alkyne rather thanphenylene units should increase the number ofadsorption sites and increase the surface area(19).NU-110[Cu3(BHEHPI);BHEHPI6–=5,5′,5′′-((((benzene-1,3,5-triyltris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))-tris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))triisophthalate],whose organiclinker is replete with such edges,displayed a sur-face area of7140m2/g(Table1)(7,17,20–32).For many practical purposes,such as storinggases,calculating the surface area per volumeis more relevant.By this standard,the value forMOF-5,2200m2/cm3,is among the very bestreported for MOFs(for comparison,the value forNU-110is1600m2/cm3).Note that the externalsurface area of a nanocube with edges measuring3nm would be2000m2/cm3.However,nano-crystallites on this scale with“clean”surfaceswould immediately aggregate,ultimately leavingtheir potential high surface area inaccessible.Expansion of Structures by a Factor of2to17A family of16cubic MOFs—IRMOF-1[alsoknown as MOF-5,which is the parent MOF ofthe isoreticular(IR)series]to IRMOF-16—withthe same underlying topology(isoreticular)wasmade with expanded and variously functionalizedorganic linkers(figs.S2and S3)(1,5).This de-velopment heralded the potential for expandingand functionalizing MOFs for applications in gasstorage and separations.The same work demon-strated that a large number of topologically iden-tical but functionally distinctive structures can bemade.Note that the topology of these isoreticularMOFs is typically represented with a three-lettercode,pcu,which refers to its primitive cubic net(33).One of the smallest isoreticular structuresof MOF-5is Zn4O(fumarate)3(34);one of thelargest is IRMOF-16[Zn4O(TPDC)3;TPDC2–=terphenyl-4,4′′-dicarboxylate](5)(fig.S2).In thisexpansion,the unit cell edge is doubled and itsvolume is increased by a factor of8.The degreeof interpenetration,and thus the porosity and den-sity of these materials,can be controlled by chang-ing the concentration of reactants,temperature,orother experimental conditions(5).The concept of the isoreticular expansion isnot simply limited to cubic(pcu)structures,asillustrated by the expansion of MOF-177to giveMOF-180[Zn4O(BTE)2]and MOF-200,whichuse larger triangular organic linkers(qom net;Fig.3A and fig.S4)(15,17).Contrary to the MOF-5type of expanded framework,expanded structuresof MOF-177are noninterpenetrating despite thehigh porosity of these MOFs(89%and90%forMOF-180and MOF-200,respectively).Theseresults highlight the critical role of selectingtopology.Another MOF of interest is known as HKUST-1[Cu3(BTC)2;BTC3–=benzene-1,3,5-tricarboxylate](35);it is composed of Cu paddlewheel[Cu2(CO2)4]SBUs(Fig.2A)and a tritopic organic linker,BTC3–.Several isoreticular structures have been madeby expansion with TA TB3–[4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tribenzoate],TA TAB3–[4,4′,4′′-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoate],TTCA3–[triphenylene-2,6,10-tricarboxylate],HTB3–[4,4′,4′′-(1,3,3a1,4,6,7,9-heptaazaphenalene-2,5,8-triyl)tribenzoate],and BBC3–linkers(tbonet;Fig.3B,fig.S1and S5,and tables S1andS2)(21,36–39).The cell volume for the largestreported member[MOF-399,Cu3(BBC)2]is17.4times that of HKUST-1.MOF-399has thehighest void fraction(94%)and lowest density(0.126g/cm3)of any MOF reported to date(21).Cu paddlewheel units are also combined withvarious lengths of hexatopic linkers to form an-other isoreticular series.The first example of oneof these MOFs is Zn3(TPBTM)[TPBTM6–=5,5′,5′′-((benzene-1,3,5-tricarbonyl)tris(azanediyl))triisophthalate],which has a ntt net(40).Shortlyafter this report,several isoreticular MOF struc-tures were synthesized(Fig.3C and fig.S6)(19,20,24,41–48):Cu3(TPBTM),Cu3(TDPA T),NOTT-112[Cu3(BTPI)],NOTT-116[also knownas PCN-68;Cu3(PTEI)],PCN-61[Cu3(BTEI)],PCN-66[Cu3(NTEI)],PCN-69[also known asNOTT-119;Cu3(BTTI)],PCN-610[also knownas NU-100;Cu3(TTEI)],NU-108[Cu3(BTETCA)],NU-109[Cu3(BNETPI)],NU-110,and NU-111[Cu3(BHEI)]TDPA T6–=5,5′,5′′-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))triisophthalate;BTPI6–=5,5′,5′′-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))triisophthalate;PTEI6–=5,5′,5′′-((benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))triisophthalate;BTEI6–=5,5′,5′′-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))triisophthalate;NTEI6–=5,5′,5′′-((nitrilotris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))triisophthalate;BTTI6–=5,5′,5′′-(benzene-1,3,5-triyl-tris(biphenyl-4,4′-diyl))triisophthalate;TTEI6–=5,5′,5′′-(((benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))triisophthalate;BTETCA6–=5′,5′′′′,5′′′′′′′-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tris(([1,1′:3′,1′′-terphenyl]-4,4′′-dicarboxylate));BNETPI6–=5,5′,5″-(((benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tris(benzene-4,1-diyl))tris(buta-1,3-diyne-4,1-diyl))triisophthalate;BHEI6–=5,5′,5″-(benzene-1,3,5-triyl-tris(buta-1,3-diyne-4,1-diyl))triisophthalate].Isoreticularmaterials are not necessarily expansions of theoriginal parent MOF,as exemplified by NU-108,because the ntt family has a linker(BTETCA6–)with two branching points and two kinds of links(figs.S1B and S7).A wide variety of metal ions form metal-carboxylate units,and isostructural MOFs can besynthesized by replacing the metal ions in theinorganic SBUs.Indeed,after the appearance ofHKUST-1[Cu3(BTC)2],an isostructural series ofHKUST-1[M3(BTC)2,where M=Zn(II),Fe(II),Mo(II),Cr(II),Ru(II)]was prepared by sever-al groups(fig.S5)(49–53).In the same way as SCIENCE VOL34130AUGUST20131230444-3REVIEWABDCZn 4O(CO 2)6Cu 2(CO 2)4Cu 2(CO 2)4Zn 4O(BTB)2MOF-177 (qom )Cu 3(BTC)2, HKUST -1MOF-199 (tbo )Cu 3(BBC)2,MOF-399 (tbo )Cu 3(TATB)2, PCN-6’ (tbo )Zn 4O(BTE)2MOF-180 (qom )Zn 4O(BBC)2MOF-200 (qom )× 1.820 Å× 2.7Tritopic linker20 Å× 5.5× 17.4Hexatopic linker30 Å× 2.2× 6.0× 6.5× 16.130 ÅTetratopic linkerCu 3(TDPAT) (ntt )Cu 3(NTEI),PCN-66 (ntt )Cu 3(BHEHPI),NU-110 (ntt )Mg 3O 3(CO 2)3Mg 2(DOT), Mg-MOF-74(IRMOF-74-I) (etb )Mg 2(DH11PhDC),IRMOF-74-XI (etb )Mg 2(DH5PhDC),IRMOF-74-V (etb )Tritopic linkerFig. 3.Isoreticular expansion of metal-organic frameworks with qom,tbo,ntt,and etb nets.(A to D )The isoreticular (maintaining same topology)expansion of archetypical metal-organic frameworks resulting from discrete [(A),(B),and (C)]and rod inorganic SBUs (D)combined with tri-,hexa-,and tetratopic organic linkers to obtain MOFs in qom (A),tbo (B),ntt (C),and etb (D)nets,respectively.Each panel shows a scaled comparison of the smallest,medium,and largest crystalline structures of MOFs representative of these nets.The large yellow and green spheres represent the largest sphere that would occupy the cavity.Numbers above each arrow represent the degree of volume expansion from the smallest framework.Color code is same as in Fig.2;hydrogen atoms are omitted for clarity.30AUGUST 2013VOL 341SCIENCE1230444-4REVIEWdiscrete inorganic SBUs,the infinite inorganic rod-type SBUs were also used to synthesize isostructural MOF-74[Zn 2(DOT);DOT =dioxidoterephthalate](54)using divalent metal ions such as Mg,Co,Ni,and Mn (fig.S8)(55).Exceptionally Large Pore AperturesPore openings of MOFs are typically large enough (up to 2nm)to accommodate small molecules,but rarely are they of appropriate size to permit inclusion of large molecules such as proteins.The best way to increase pore apertures is to use infinite rod-shaped SBUs with linkers of arbitrary length providing periodicity in the other two di-mensions,which does not allow for interpene-trating structures.This strategy was implemented by expanding the original phenylene unit of MOF-74[M 2(DOT);M 2+=Zn,Mg]structure (54)to 2,3,4,5,6,7,9,and 11phenylene units [DH2PhDC 4–to DH11PhDC 4–,respectively;Fig.2B,Fig.3D,and figs.S1B and S8](22).Crystal structures revealed that pore apertures for this series of MOF-74struc-tures (termed IRMOF-74-I to IRMOF-74-XI)ranged from 14to 98Å.The presence of the large pore apertures was also confirmed by transmission elec-tron microscopy (TEM)and scanning electron microscopy (SEM)observation as well as argon adsorption measurements of the guest-free mate-rials.As expected,the pore aperture of IRMOF-74-IX is of sufficient size to allow for green fluorescent protein (barrel structure with diameter of 34Åand length of 45Å)to pass into the pores without unfolding.More important,the large pore aperture is of benefit to the surface modification of the pores with various functionalities without sacrificing the porosity (22).An oligoethylene glycol –functionalized IRMOF-74-VII [Mg 2(DH7PhDC-oeg)]allows in-clusion of myoglobin,whereas IRMOF-74-VII with hydrophobic hexyl chains showed a negli-gible amount of inclusion.High Thermal and Chemical StabilityBecause MOFs are composed entirely of strong bonds (e.g.,C-C,C-H,C-O,and M-O),they show high thermal stability ranging from 250°to 500°C (5,56–58).It has been a challenge to make chem-ically stable MOFs because of their susceptibility to link-displacement reactions when treated with solvents over extended periods of time (days).The first example of a MOF with exceptional chemical stability is zeolitic imidazolate framework –8[ZIF-8,Zn(MIm)2;MIm –=2-methylimidazolate],which was reported in 2006(56).ZIF-8is unaltered after immersion in boiling methanol,benzene,and water for up to 7days,and in concentrated sodium hydroxide at 100°C for 24hours.201220102008200620041999010002000300040005000600070008000Typical conventionalporous materialsMOFsZ e o l i t e s (0.30)S i l i c a s (1.15)C a r b o n s (0.60)MIL-101(2.15)MIL-101 (2.00)MOF-177 (1.59)NOTT-119 (2.35)MOF-210 (3.60)NU-100 (2.82)NU-110(4.40)UMCM-2(2.32)DUT-49(2.91)MOF-5(1.04)MOF-5 (1.20)MOF-5(1.56)MOF-177 (2.00)IRMOF-20 (1.53)MOF-5 (1.48)U M C M -1 (2.24)P C N -6 (1.41)M I L -100 (1.10)M O F -200 (3.59)B i o -M O F -100 (4.30)N O T T -112 (1.59)D U T -23(C o ) (2.03)Fig.4.Progress in the synthesis of ultrahigh-porosity MOFs.BET surface areas of MOFs and typical conventional materials were estimated from gas adsorption measurements.The values in parentheses represent the pore volume (cm 3/g)of these materials.Table 1.Typical properties and applications of metal-organic frameworks.Metal-organic frameworks exhibiting the lowest and highest values for the indicated property,and those reported first for selected applications,are shown.Property or applicationCompound Achieved value or year of reportReference Lowest reported value DensityMOF-3990.126g/cm 3(21)Highest reported value Pore apertureIRMOF-74-XI 98Å(22)Number of organic linkers MTV-MOF-58(7)Degrees of interpenetration Ag 6(OH)2(H 2O)4(TIPA)554(23)BET surface area NU-1107140m 2/g (20)Pore volumeNU-110 4.40cm 3/g (20)Excess hydrogen uptake (77K,56bar)NU-1009.0wt%(24)Excess methane uptake (290K,35bar)PCN-14212mg/g (25)Excess carbon dioxide uptake (298K,50bar)MOF-2002347mg/g (17)Proton conductivity (98%relative humidity,25°C)(NH 4)2(ADP)[Zn 2(oxalate)3]·3H 2O8×10−3S/cm (26)Charge mobilityZn 2(TTFTB)0.2cm 2/V·s (27)Lithium storage capacity (after 60cycles)Zn 3(HCOO)6560mAh/g(28)Earliest reportCatalysis by a MOFCd(BPy)2(NO 3)21994(29)Gas adsorption isotherm and permanent porosity MOF-21998(12)Asymmetric catalysis with a homochiral MOF POST-12000(31)Production of open metal site MOF-112000(30)PSM on the organic linkerPOST-12000(31)Use of a MOF for magnetic resonance imagingMOF-732008(32) SCIENCE VOL 34130AUGUST 20131230444-5REVIEWMOFs based on the Zr(IV)cuboctahedral SBU (Fig.2A)also show high chemical stability;UiO-66[Zr 6O 4(OH)4(BDC)6]and its NO 2-and Br-functionalized derivatives demonstrated high acid (HCl,pH =1)and base resistance (NaOH,pH =14)(57,58).The stability also remains when tetratopic organic linkers are used;both MOF-525[Zr 6O 4(OH)4(TpCPP-H 2)3;TpCPP =tetra-para -carboxyphenylporphyrin]and 545[Zr 6O 8(TpCPP-H 2)2]are chemically stable in methanol,water,and acidic conditions for 12hours (59).Furthermore,a pyrazolate-bridged MOF [Ni 3(BTP)2;BTP 3–=4,4′,4″-(benzene-1,3,5-triyl)tris(pyrazol-1-ide)]is stable for 2weeks in a wide range of aqueous solutions (pH =2to 14)at 100°C (60).The high chemical stability observed in these MOFs is expected to enhance their per-formance in the capture of carbon dioxide from humid flue gas and extend MOFs ’applications to water-containing processes.Postsynthetic Modification (PSM):Crystals as MoleculesThe first very simple,but far from trivial,example of PSM was with the Cu paddlewheel carboxylate MOF-11[Cu 2(A TC);A TC 4–=adamantane-1,3,5,7-tetracarboxylate](30).As-prepared Cu atoms are bonded to four carboxylate O atoms,and the co-ordination shell is completed typically with coor-dinated water (Fig.2A).Subsequent removal of the water from the immobilized Cu atom leaves a coordinatively unsaturated site (“open metal site ”).Many other MOFs with such sites have now been generated and have proved to be exceptionally favorable for selective gas uptake and catalysis (61–63).The first demonstration of PSM on the or-ganic link of a MOF was reported in 2000for a homochiral MOF,POST-1[Zn 3(m 3-O)(D-PTT)6;D-PTT –=(4S ,5S )-2,2-dimethyl-5-(pyridin-4-ylcarbamoyl)-1,3-dioxolane-4-carboxylate](31).It involved N -alkylation of dangling pyridyl func-tionalities with iodomethane and 1-iodohexane to produce N -alkylated pyridinium ions exposed to the pore cavity.More recently,PSM was applied to the dan-gling amine group of IRMOF-3[Zn 4O(BDC-NH 2)3]crystals (6).The MOF was submerged in a dichloromethane solution containing acetic anhy-dride to give the amide derivative in >80%yield.Since then,a large library of organic reactions have been used to covalently functionalize MOF backbones (table S4)(64,65).UMCM-1-NH 2[(Zn 4O)3(BDC-NH 2)3(BTB)4]was also acylated with benzoic anhydride to produce the corresponding amide functionality within the pores (66).The structures of both IRMOF-3and UMCM-1-NH 2after modification showed increased hydrogen uptake relative to the parent MOFs,even though there was a reduction in overall surface area (66).PSM has also been used to dangle catalytically active centers within the pores.In an example reported in 2005,a Cd-based MOF built from 6,6′-dichloro-4,4′-di(pyridin-4-yl)-[1,1′-binaphthalene]-2,2′-diol (DCDPBN),[CdCl 2(DCDPBN)],used orthogonal dihydroxy functionalities to coordinate titanium isopropoxide [Ti(O i Pr)4],thus yielding a highly active,enantio-selective asymmetric Lewis acid catalyst (67).UMCM-1-NH 2was also functionalized in such a manner to incorporate salicylate chelating groups,which were subsequently metallated with Fe(III)and used as a catalyst for Mukaiyama aldol reac-tions over multiple catalytic cycles without loss of activity or crystallinity (68).Indeed,the remarkable retention of MOF crystallinity and porosity after undergoing the transformation reactions clearly dem-onstrates the use of MOF crystals as molecules (69).Catalytic Transformations Within the Pores The high surface areas,tunable pore metrics,and high density of active sites within the very open structures of MOFs offer many advantages to their use in catalysis (table S5).MOFs can be used to support homogeneous catalysts,stabi-lize short-lived catalysts,perform size selectiv-ity,and encapsulate catalysts within their pores (70).The first example of catalysis in an ex-tended framework,reported in 1994,involved the cyanosilylation of aldehydes in a Cd-based frame-work [Cd(BPy)2(NO 3)2;BPy =4,4′-bipyridine]as a result of axial ligand removal (29).This study also highlighted the benefits of MOFs as size-selective catalysts by excluding large sub-strates from the pores.In 2006,it was shown that removal of solvent from HKUST-1exposes open metal sites that may act as Lewis acid catalysts (71).MIL-101[Cr 3X(H 2O)2O(BDC)3;X =F,OH]and Mn-BTT {Mn 3[(Mn 4Cl)3(BTT)8]2;BTT 3–=5,5′,5″-(benzene-1,3,5-triyl)tris(tetrazol-2-ide)}have also been iden-tified as Lewis acid catalysts in which the metal oxide unit functions as the catalytic site upon lig-and removal (62,72).In addition,alkane oxida-tion,alkene oxidation,and oxidative coupling reactions have also been reported;they all rely on the metal sites within the SBUs for catalytic ac-tivity (73–75).The study of methane oxidation in vanadium-based MOF-48{VO[BDC-(Me)2];Me =methyl}is promising because the catalytic turnover and yield for this oxidation far exceed those of the analogous homogeneous catalysts (73).One early example of the use of a MOF as a het-erogeneous catalyst is PIZA-3[Mn 2(TpCPP)2Mn 3],which contains a metalloporphyrin as part of the framework (76).PIZA-3is capable of hydrox-ylating alkanes and catalyzes the epoxidation of olefins.Schiff-base and binaphthyl metal complexes have also been incorporated into MOFs to achieve olefin epoxidation and diethyl zinc (ZnEt 2)addi-tions to aromatic aldehydes,respectively (67,77).The incorporation of porphyrin units within the pores of MOFs can be accomplished during the synthesis (a “ship-in-a-bottle ”approach that cap-tures the units as the pores form),as illustrated for the zeolite-like MOF rho -ZMOF [In(HImDC)2·X;HImDC 2–=imidazoledicarboxylate,X –=coun-teranion](78).The pores of this framework accom-modate high porphyrin loadings,and the pore aperture is small enough to prevent porphyrin fromleaching out of the MOF.The porphyrin metal sites were subsequently metallated and used for the oxidation of cyclohexane.The same approach has been applied to several other systems in which polyoxometalates are encapsulated within MIL-101(Cr)and HKUST-1for applications in the oxidation of alkenes and the hydrolysis of esters in excess water (79,80).Integration of nanoparticles for catalysis by PSM has been carried out to enhance particle stability or to produce uniform size distributions.Palladium nanoparticles were incorporated with-in MIL-101(Cr)for cross-coupling reactions (81,82).Most recently,a bifunctional catalytic MOF {Zr 6O 4(OH)4[Ir(DPBPyDC)(PPy)2·X]6;DPBPyDC 2–=4,4′-([2,2′-bipyridine]-5,5′-diyl)dibenzoate,PPy =2-phenylpyridine}capable of water-splitting reactions was reported (83).This MOF uses the organic linker and an encapsulated nanoparticle to transfer an electron to a proton in solution,leading to hydrogen evolution.Gas Adsorption for Alternative Fuels and Separations for Clean AirMuch attention is being paid to increasing the storage of fuel gases such as hydrogen and meth-ane under practical conditions.The first study of hydrogen adsorption was reported in 2003for MOF-5(84).This study confirmed the potential of MOFs for application to hydrogen adsorption,which has led to the reporting of hydrogen ad-sorption data for hundreds of MOFs (85).In gen-eral,the functionality of organic linkers has little influence on hydrogen adsorption (86),whereas increasing the pore volume and surface area of MOFs markedly enhances the gravimetric hydro-gen uptake at 77K and high pressure,as exem-plified by the low-density materials:NU-100and MOF-210exhibit hydrogen adsorption as high as 7.9to 9.0weight percent (wt%)at 56bar for both MOFs and 15wt%at 80bar for MOF-210(17,24).However,increasing the surface area is not always an effective tool for increasing the volumetric hydrogen adsorption,which can be accomplished by increasing the adsorption enthalpy of hy-drogen (Q st )(87).In this context,open metal sites have been suggested and used to enhance the hydrogen uptake capacity and to improve Q st (61,85).Two MOFs with this characteristic,Zn 3(BDC)3[Cu(Pyen)][Pyen 2–=5,5′-((1E ,1′E )-(ethane-1,2-diyl-bis(azanylylidene))bis(methanylylidene))bis(3-methylpyridin-4-ol)]and Ni-MOF-74,have the highest reported initial Q st values:15.1kJ/mol and 12.9kJ/mol,respectively (58,88).Metal impreg-nation has also been suggested by computation as a method for increasing the Q st values (89).Experiments along these lines show that dop-ing MOFs with alkali metal cations yields only modest enhancements in the total hydrogen up-take and Q st values (90,91).Although some chal-lenges remain in meeting the U.S.Department of Energy (DOE)system targets (5.5wt%and 40g/liter at –40°to 60°C below 100bar)for hy-drogen adsorption (85),Mercedes-Benz has al-ready deployed MOF hydrogen fuel tanks in a30AUGUST 2013VOL 341SCIENCE1230444-6REVIEW。

液相合成金纳米团簇

第23卷第10期2011年10月化　学　进　展PROGRESS IN CHEMISTRYVol.23No.10　Oct.2011 收稿:2010年12月,收修改稿:2011年3月　∗国家自然科学基金项目(No.20871112,21072001)和安徽大学211工程项目资助∗∗Corresponding author　e⁃mail:zmz@液相合成金纳米团簇∗刘　钊　金申申　朱满洲∗∗(安徽大学化学化工学院　合肥230039)摘　要　作为过渡金属团簇的一种,金纳米团簇由于具有不同于其它纳米材料的特殊物化性能,在催化、光学、电学及生物技术等领域具有潜在的应用前景。

本文综述了液相合成金纳米团簇的研究进展,主要包括有机膦化物和硫醇保护的金纳米团簇的合成方法与晶体结构,这将为金纳米团簇的研究者提供一定的参考。

关键词　金　纳米团簇　液相合成中图分类号:O614.123;O611.4　文献标识码:A　文章编号:1005⁃281X(2011)10⁃2055⁃10Liquid⁃Phase Synthesis of Gold NanoclustersLiu Zhao Jin Shenshen Zhu Manzhou ∗∗(School of Chemistry and Chemical Engineering,Anhui University,Hefei 230039,China)Abstract As a kind of transition metal nanoclusters,gold nanoclusters have potential applications incatalysis,optics,electronics and biotechnology due to the advantages of their special physical and chemical properties that are different from other nanomaterials.The progress in liquid⁃phase synthesis of gold nanoclusters issummarized here,which includes the synthetic method and crystal structure of gold clusters protected by phosphidesor thiols.We hope that this paper could be helpful for the scientists to research the gold nanoclusters in future.Key words gold;nanoclusters;liquid⁃phase synthesisContents1　Introduction2　Gold nanoclusters protected by phosphides 2.1　[Au 5(dppmH)3(dppm)](NO 3)22.2　[Au 8(PR 3)7](NO 3)22.3　[Au 9(PR 3)8](BF 4)32.4　Au 10Cl 3(PCy 2Ph)6(NO 3)(Cy =cyclohexyl)2.5　Au 11(PAr 3)7X 3(X:Cl or I)2.6　[Au 13(dppmH)6](NO 3)42.7　[Au 39(PPh 3)14Cl 6]Cl 22.8　Au 55(PPh 3)12Cl 63　Gold nanoclusters protected by thiols3.1　Au 25(SCH 2CH 2Ph)18q (q =-1or 0)3.2　[Au 25(PPh 3)10(SC n H 2n +1)5Cl 2]2+(n =2—18)3.3　Au 38(SC 2H 4Ph)243.4　Au 102(p ⁃MBA)444　Summary and outlook1　引言原子簇化学(cluster chemistry)首先由弗兰克·阿尔伯特·科顿于1966年提出,是当前材料科学、有机金属化学等学科中最前沿的领域之一。

Acta Crystallographica Section C Crystal Structure Communications

A triclinic polymorph of benzanilide:disordered molecules form hydrogen-bonded chainsKatharine F.Bowes,a Christopher Glidewell,a *John N.Low,b Janet M.S.Skakle b and James L.Wardell caSchool of Chemistry,University of St Andrews,St Andrews,Fife KY169ST,Scotland,b Department of Chemistry,University of Aberdeen,Meston Walk,Old Aberdeen AB243UE,Scotland,and c Instituto de QuõÂmica,Departamento de QuõÂmica Inorga Ãnica,Universidade Federal do Rio de Janeiro,21945-970Rio de Janeiro,RJ,BrazilCorrespondence e-mail:cg@ Received 28October 2002Accepted 1November 2002Online 10December 2002In the P 1polymorph of benzanilide or N -phenylbenzamide,C 13H 11NO,the molecules are linked into simple C (4)chains by NÐH ÁÁÁO hydrogen bonds.The molecules exhibit orienta-tional disorder,but the donor and acceptor in a given hydrogen bond may occur,independently,in either the major or the minor orientation,such that all four possible NÐH ÁÁÁO combinations have very similar geometries.The structure of this P 1polymorph can be related to that of a previously reported C 2/c polymorph.CommentThe crystal structure of benzanilide,PhNHCOPh,(I),was ®rst reported many years ago (Kashino et al.,1979).These authors reported an ambient temperature study of a C 2/c phase crystallized from ethanol,which has Z H =12with the molecules disordered across twofold rotation axes,such that the O atom and the H atom bonded to N both lie on the twofold axes.A unique H ÁÁÁO contact thus characterizes the NÐH ÁÁÁO hydrogen bonds,which link the molecules into a C (4)chain generated by translation along the shortest axis of the cell,viz.b =5.323(3)AÊ.In this paper,we report the structure of a triclinic (P 1,Z H=1)polymorph of (I),also crystallized from ethanol.In this polymorph,the molecules (Fig.1)lie in general positions,but it was clear early in the re®nement that there was some orientational disorder in the structure.Some 16%of the molecular sites are occupied by a second orientation,which isapproximately related to the major orientation by a 180 rotation of the molecule about a line in the plane of the central HNCO unit lying normal to the C14ÁÁÁC24line.Hence atoms C14and C44have almost coincident sites,as do atoms C24and C34.Similarly,atom pairs O11/O21and H11/H21occupy sites which are almost coincident (Fig.2).The molecules of (I)are linked into C (4)chains generated by translation along the [100]direction (Fig.3),and because of the close proximity of the alternative donor and acceptor sites,hydrogen bonds can be formed between any two adjacent molecules within the chain,regardless of whether they adopt the major or minor orientation (Table 2).Hence the hydrogen bonding imposes no necessary correlation between the molecular orientations at adjacent sites within the chain,although this may be imposed by non-bonded C ÁÁÁC contacts.Within the molecule of (I),the bond lengths and angles present no unusual features.The central CÐN(H)ÐC(O)ÐC fragment is essentially planar and the phenyl rings are eachActa Cryst.(2003).C 59,o1±o3DOI:10.1107/S0108270102019996#2003International Union of Crystallographyo1organic compoundsActa Crystallographica Section CCrystal Structure CommunicationsISSN0108-2701Figure 2Part of the crystal structure of (I),showing the two orientations of the molecule;the major orientation is shown with solid bonds and the minor orientation with dashed bonds.Figure 1Views of the molecule of compound (I),showing the atom-labellingscheme for (a )the major orientation and (b )the minor orientation.For the major orientation,displacement ellipsoids are drawn at the 30%probability level,but for the minor orientation,all non-H atoms were re®ned isotropically (see text).H atoms are shown as small spheres of arbitrary radii.organic compoundso2Katharine F.Bowes et al.C 13H 11NOActa Cryst.(2003).C 59,o1±o3twisted by ca 30 away from this plane (Table 1).The conformation in the P 1polymorph thus resembles that in the C 2/c polymorph,where the dihedral angles between the rings and the central unit are both ca 31 .The density reported for the C 2/c polymorph (1.321Mg m À3)is somewhat lower than that found here for the P 1form.This suggests that the P 1form may be thermo-dynamically more stable (Burger &Ramberger,1979).The ambient-temperature unit cell reported for the C 2/c poly-morph [a =24.34(4),b =5.325(3)and c =8.012(8)AÊ,and =107.2(3) ;Kashino et al.,1979]can be readily related to the P 1cell by the transformation (0,À1,0/0,0,À1/12,0,0).In the C 2/c polymorph,the molecules lie across twofold rotation axes,with the centroid of the reference molecule at (0,0.205,0.250),while in the P 1polymorph,the centroid of the reference molecule is at approximately (0.198,0.749,À0.002),so that the projections of the two structures down their short axes are very similar (Fig.4).However,alternate chains in the [100]direction in the C 2/c structure are related by the C -centring operation and hence suffer a shift of b 2between adjacent chains in this direction,whereas no such shifts occur in the P 1polymorph.In addition to these translations,the very different disorder ratios (50:50in C 2/c and 84:16in P 1)effectively preclude the possibility of a simple displacive phase transformation between the two polymorphs,as this would require at least 34%of the molecules to change orientation on conversion ofeither phase to the other.Since the molecules are ca 11.2AÊin length,and longer if the van der Waals surfaces are included,the end-over-end rotation involved in this change of orienta-tion would require each such molecule to sweep out,unhin-dered,a disc of area nearly 100AÊ2.As in the P 1polymorph,there is no necessary correlation between the orientations of adjacent molecules in the C 2/c polymorph imposed by the hydrogen bonding.However,it was found by Kashino et al.(1979)that non-bonded C ÁÁÁC contacts imposed correlation within,but not between,the [010]chains.Kashino et al.(1979)discussed the C 2/c structure in terms of the fully ordered structures which could arise in each of the subgroups of C 2/c (Cc ,C 1,P 21/c and P 21/n );the representation in Fig.4(b )is,in fact,the C 1substructure.In our recent structural studies,we have encountered several examples of concomitant polymorphism.Thus,when crystallized from ethanol,2-iodo-4-nitroaniline yields a mix-ture of triclinic (P 1,Z H =1)and orthorhombic (Pbca ,Z H =1)crystals which have slightly different colours (McWilliam et al.,2001).Crystallization of ethyl N -(2-amino-6-benzyloxy-5-nitrosopyrimidin-2-yl)-3-aminopropanoate from acetonitrile±ethanol±water (1:1:1by volume)yields a mixture of two monoclinic polymorphs,one blue (P 21/c ,Z H =1)and the other pink (P 21,Z H =2)(Quesada et al.,2002),where the confor-mations of the three independent molecules are all different,so that these concomitant polymorphs are also conformational polymorphs.The 1:1adduct formed between (S )-malic acid and 4,4H -bipyridyl crystallizes from methanol as a mixture of triclinic (P 1,Z H =1)and monoclinic (C 2,Z H =1)polymorphs (Farrell et al.,2002).Finally,benzanilide crystallizes from ethanol in both a monoclinic form (C 2/c ,Z H =12;Kashino et al.,1979)and the triclinic form (P 1,Z H=1)reported here.We emphasize that in none of these systems had there been any attempt to engineer such polymorphic behaviour,nor was this behaviour being speci®cally sought after.Instead,each pair of polymorphs was identi®ed serendipitously.In the cases of 2-iodo-4-nitroaniline and the nitrosopyrimidine,the iden-ti®cation of the two forms was facilitated by their different colours,but in the other examples,identi®cationdependedFigure 4Projections of the structures of (I),showing (a )the P 1polymorph projected on to the bc plane (for the sake of clarity,only the major orientation is shown),and (b )the C 2/c polymorph,projected on to the ac plane (for the sake of clarity,only one orientation is shown).In each projection,H atoms bonded to C atoms have been omitted forclarity.Figure 3Part of the crystal structure of (I),showing the formation of a C (4)chain along [100].For the sake of clarity,only the major orientation is shown and H atoms bonded to C atoms have been omitted.Atoms marked with an asterisk (*)or hash (#)are at the symmetry positions (1+x ,y ,z )and (x À1,y ,z ),respectively.solely upon careful scrutiny of the crystalline samples and the observation of more than one crystal habit,followed in every case by careful manual separation.Our identi®cation,essentially by chance,of four such examples within a rather short space of time suggests to us that the phenomenon of concomitant polymorphism may,in fact,be a rather common one,certainly far more common than the current literature [for a review,see Bernstein et al.(1999)]tends to suggest,but one which goes largely unnoticed.On the other hand,we note the recent report on 3,6,13,16-tetra-bromo-2,7,12,17-tetrapropylporphycene,where monoclinic prisms and triclinic plates crystallize concurrently from di-chloromethane±hexane (Aritome et al.,2002).ExperimentalA commercial sample of benzanilide (Aldrich)was crystallized froman ethanol solution at ambient temperature.Crystal dataC 13H 11NO M r =197.23Triclinic,P 1a =5.3406(5)A Êb =7.7727(7)A Êc =12.3901(15)A Ê =72.702(3)=79.389(3) =89.914(5)V =481.89(9)AÊ3Z =2D x =1.359Mg m À3Mo K radiationCell parameters from 2140re¯ections =3.5±27.5 "=0.09mm À1T =120.0(1)K Block,colourless0.08Â0.06Â0.04mmData collectionNonius KappaCCD area-detector diffractometer9scans,and 3scans with offsets Absorption correction:multi-scan (DENZO ±SMN ;Otwinowski &Minor,1997)T min =0.989,T max =0.9977033measured re¯ections2140independent re¯ections 1092re¯ections with I >2'(I )R int =0.079 max =27.5 h =À636k =À10310l =À15315Re®nementRe®nement on F 2R [F 2>2'(F 2)]=0.061wR (F 2)=0.160S =0.962140re¯ections 159parametersH-atom parameters constrained w =1/['2(F o 2)+(0.0761P )2]where P =(F o 2+2F c 2)/3(Á/')max <0.001Á&max =0.27e A ÊÀ3Á&min =À0.25e AÊÀ3Space group P 1was selected and con®rmed by the subsequent structure analysis.The ADDSYM option in PLATON (Spek,2002)revealed no additional symmetry.For the minor orientational component,the two rings were constrained to be planar regularhexagons,with CÐC distances of 1.39AÊ,and the remaining distances involving C,N and O atoms were tied to the corresponding distances in the major component.The non-H atoms in the minor component were all re®ned isotropically.A common isotropic displacement parameter was applied to atoms C31±C36,a second common isotropic displacement parameter to atoms C41±C46,and individual isotropic parameters to atoms N31,C37and O31.The site-occupancy factors for the two orientations then re®ned to 0.839(5)and 0.161(5).The H atoms were treated as riding,with CÐH distances of0.95AÊand NÐH distances of 0.88A Ê.Data collection:KappaCCD Server Software (Nonius,1997);cell re®nement:DENZO ±SMN (Otwinowski &Minor,1997);data reduction:DENZO ±SMN ;program(s)used to solve structure:SHELXS 97(Sheldrick,1997);program(s)used to re®ne structure:SHELXL 97(Sheldrick,1997);molecular graphics:PLATON (Spek,2002);software used to prepare material for publication:SHELXL 97and PRPKAPPA (Ferguson,1999).The X-ray data were collected at the EPSRC X-ray Crys-tallographic Service,University of Southampton,England;the authors thank the staff for all their help and advice.JNL thanks NCR Self-Service,Dundee,for grants which have provided computing facilities for this work.JL W thanks CNPq and FAPERJ for ®nancial support.Supplementary data for this paper are available from the IUCr electronic archives (Reference:SK1598).Services for accessing these data are described at the back of the journal.ReferencesAritome,I.,Shimakoshi,H.&Hisaeda,Y.(2002).Acta Cryst.C 58,o563±o564.Bernstein,J.,Davey,R.J.&Henck,J.-O.(1999).Angew.Chem.Int.Ed.38,3440±3461.Burger,A.&Ramberger,R.(1979).Mikrochim.Acta ,2,259±271.Farrell,D.M.M.,Ferguson,G.,Lough,A.J.&Glidewell,C.(2002).Acta Cryst.B 58,530±544.Ferguson,G.(1999).PRPKAPPA .University of Guelph,Canada.Kashino,S.,Ito,K.&Haisa,M.(1979).Bull.Chem.Soc.Jpn ,52,365±369.McWilliam,S.A.,Skakle,J.M.S.,Low,J.N.,Wardell,J.L.,Garden,S.J.,Pinto,A.C.,Torres,J.C.&Glidewell,C.(2001).Acta Cryst.C 57,942±945.Nonius (1997).KappaCCD Server Software .Windows 3.11Version.Nonius BV ,Delft,The Netherlands.Otwinowski,Z.&Minor,W.(1997).Methods in Enzymology ,Vol.276,Macromolecular Crystallography ,Part A,edited by C.W.Carter Jr &R.M.Sweet,pp.307±326.New York:Academic Press.Quesada,A.,Marchal,A.,Melguizo,M.,Nogueras,M.,SaÂnchez,A.,Low,J.N.,Cannon,D.,Farrell,D.M.M.&Glidewell,C.(2002).Acta Cryst.B 58,300±315.Sheldrick,G.M.(1997).SHELXS 97and SHELXL 97.University ofGoÈttingen,Germany.Spek,A.L.(2002).PLATON.Version of June 2002.University of Utrecht,The Netherlands.Acta Cryst.(2003).C 59,o1±o3Katharine F.Bowes et al.C 13H 11NOo3organic compoundsTable 2Hydrogen-bonding geometry (AÊ, ).D ÐH ÁÁÁA D ÐH H ÁÁÁA D ÁÁÁA D ÐH ÁÁÁA N11ÐH11ÁÁÁO11i0.88 2.31 3.141(4)157N11ÐH11ÁÁÁO31i 0.88 2.34 3.13(2)150N31ÐH31ÁÁÁO11i 0.88 2.31 3.17(3)165N31ÐH31ÁÁÁO31i0.882.373.24(3)172Symmetry code:(i)1 x Y y Y z .Table 1Selected torsion angles ( ).C11ÐN11ÐC17ÐC21À179.8(3)C12ÐC11ÐN11ÐC1732.5(5)N11ÐC17ÐC21ÐC22À150.7(3)。

金纳米簇金属有机骨架

金纳米簇金属有机骨架English.Gold nanoclusters (Au NCs) are discrete atomically precise subnanometer-sized gold particles with unique physicochemical properties that differ significantly from their bulk counterparts or larger nanoparticles. They have attracted considerable attention due to their intriguing optical, electronic, catalytic, and biological properties, which make them promising candidates for various applications in sensing, catalysis, bioimaging, and theranostics. Metal-organic frameworks (MOFs) are a class of highly porous crystalline materials constructed from inorganic metal ions or clusters coordinated to organic ligands. MOFs have gained significant interest due to their exceptional structural diversity, tunable porosity, and diverse functionalities. The combination of Au NCs and MOFs has emerged as a promising strategy to create multifunctional hybrid materials with synergistic properties.The integration of Au NCs into MOFs offers several advantages. Firstly, Au NCs can serve as active siteswithin the MOFs, enhancing their catalytic activity, electrochemical performance, and sensing capabilities. The small size and high surface area of Au NCs provide abundant active sites for catalytic reactions, while the well-defined structure and composition of Au NCs enable precise control over their catalytic properties. Secondly, Au NCs can enhance the optical properties of MOFs, leading to improved light absorption, emission, and sensing performance. The localized surface plasmon resonance (LSPR) of Au NCs can interact with light, resulting in enhanced light scattering and absorption, which can be exploited for sensing applications. Thirdly, Au NCs can improve the stability and functionality of MOFs. The incorporation of Au NCs into MOFs can enhance their thermal, chemical, and mechanical stability, making them more suitable for practical applications.The synthesis of Au NC@MOF composites can be achieved through various methods, including direct synthesis, post-synthetic modification, and in situ growth. Direct synthesis involves the simultaneous formation of Au NCs and MOFs in a single step, while post-synthetic modification involves the introduction of Au NCs into pre-synthesized MOFs. In situ growth refers to the formation of Au NCs within the pores or on the surface of MOFs during the MOF synthesis process. The choice of synthesis method depends on the desired properties and applications of the resulting Au NC@MOF composites.应用。

聚合物稳定的金纳米粒子直接催化葡萄糖氧化

聚合物稳定的金纳米粒子直接催化葡萄糖氧化
2016-06-10 12:39来源：内江洛伯尔材料科技有限公司作者：研发部
金纳米粒子直接催化葡萄糖氧化
近年来, Au催化剂用于有机物液相选择氧化反应成为催化研究的热点. Prati 等, Biella等和Comotti等分别研究了活性炭等载体担载的Au催化剂对醇、醛和
葡萄糖等液相选择氧化的催化性能. Demirel等报道了活性炭担载Au催化剂对单元醇和多元醇的选择氧化性能. Corma研究组和Hutchings研究组分别报道了担载型Au-Pd催化剂对烃及醇的选择氧化. 这些选择氧化反应均以分子氧为氧化剂, 无需
其它有机溶剂, 属于环境友好的绿色过程. 研究表明, 担载型Au催化剂具有催化
活性高、产物选择性好、反应条件温和等优点. 然而, 受载体本性及结构的限制, 纳米Au粒子并不能在载体上保持持久稳定, 在反应过程中不可避免地存在活性组分
的流失, 故担载型Au催化剂在重复使用时, 活性明显下降. 另一方面, 目前已报
道的有关研究均不能排除担载型Au催化剂的高活性实际上是由于分散到反应体系
中的纳米Au粒子在起催化作用的可能性.
烟台大学应用催化研究所索掌怀等人采用化学还原法制备了聚乙烯吡
咯烷酮(PVP)稳定的纳米Au溶胶, 这种Au溶胶在葡萄糖空气氧化制葡萄糖酸反应中具有良好的催化性能. 考察了PVP加入量和氯金酸前驱液的浓度对反应活性的影响. 紫外-可见吸收光谱和透射电镜分析结果表明, 含有较小Au粒子的Au溶胶体系具有较高的催化活性. 当PVP/Au质量比为40, 氯金酸浓度为100 μg/ml时, 得到稳定的Au溶胶体系具有金粒子尺寸小、分布均匀的特点, 对葡萄糖氧化反应活性高, 葡萄糖的转化率达到54.4%.。