苝酰亚胺
苝酰亚胺分子的制备
苝酰亚胺分子的制备
苯酰亚胺是一种重要的有机化合物，它可以通过多种方法进行
制备。
以下是其中一种常见的制备方法：
首先，你需要将苯甲醛和氨水混合，在室温下搅拌。
这会导致
苯甲醛与氨水发生反应，生成苯酰亚胺。
这个反应可以用下面的方
程式表示：
C6H5CHO + NH3 + H2O → C6H5C(O)NH2 + H2O.
在这个反应中，苯甲醛中的羰基和氨水中的氨基结合，生成了
苯酰亚胺。
需要注意的是，这个反应通常需要在较低的温度下进行，并且需要搅拌以保证反应充分进行。
除了上述方法，苯酰亚胺还可以通过其他途径进行制备，比如
使用苯甲酸和氨基化合物进行反应，或者利用其他酰胺化合物进行
反应等等。
这些方法都有各自的优缺点，可以根据具体情况选择合
适的方法进行制备。
总的来说，苯酰亚胺是一种重要的有机化合物，其制备方法多
种多样，可以根据实际需求选择合适的方法进行制备。
希望以上信息能够对你有所帮助。
乙酸介质中构筑苝酰亚胺染料长纳米线
乙 酸 介 质 中构 筑 茈 酰 亚 胺 染 料 长 纳 米 线
曹亚锋 ，解波雨 ，孙景志
（ 江大学高分子科学与工程学系 ， 浙 教育部高分子合成与功能构造重点实验室 ，杭州 ３０ ２ ） １０７ 摘要 合成 ＿一种带酰胺基的＿ 酰亚胺 ．紫外一 － ｒ 茈 可见光谱表明 ， 该化合物在乙酸和体 积分数大于 ４ ％ 的乙酸 ０
变过程．
关键词
纳 米 线 ； 酰亚 胺 ；分 子排 列 茈 ０ ４ ６３ 文献标识码 Ａ 文章 编 号 ０５ － ９ （０７ １—９４０ ２ １０ ０ ２ ０ ）０ １４ － ７ ４
中 图 分 类号
有 机半 导体在 电致发 光 与显示 器件 、 阳能 电池 和薄 膜 晶体 管 等领 域 的应 用 已 引起 了广 泛关 注 ， 太
仪上测定； 样品的微观形态分别在 Ｊ Ｏ Ｍ ５０型扫描 电子显微镜和 ＪＭ ０Ｃ Ｅ ＬＪ ５ １ Ｓ Ｅ ２０ Ｘ型透射 电子显微镜
上进行 观察 ．Biblioteka １２ 实验过 程 ．茈 酰亚胺 衍生 物 １的合成路 线见 Ｓ ｈｍｅ１ 实验 过程参 见文 献 ［ ５ ． ｃｅ ， ４， ］
核磁共 振 氢谱 、 外吸 收 光谱 、 外一 见 （ Ｖ Ｖｓ 吸 收 光谱 和 元素 分 析分 别 在 Ｍｅｃｒ ｌ ０ 红 紫 可 ｕ — ｉ） ｒ ｙｐｕ ３０ ｕ ｓ
型核磁 共振 波谱 仪 、Ｂｕ ｅ Ｉ Ｆ Ｉ ｒｋ ｒＶ型 Ｔ Ｒ分 析 仪 、 Ｅ Ｌ ｍ ｄ ０紫外一 见光谱 仪和 Ｐ ４ Ｃ型元 素分析 Ｉ Ｐ ａ ｂ ａ２ 可 Ｅ２ ０
产 物为红 褐色 固体 ， 收率 约为 ３．％ ． Ｈ Ｎ ８ １ ＭＲ（ 代氯 仿／ 代三 氟 乙酸 ） ６ ８７ ８８ （ 环 氘 氘 ， ： ．７～ ．０ 茈
苝酰亚胺自由基
苝酰亚胺自由基苝酰亚胺自由基是有机化学中的一种重要的中间体，具有广泛的应用价值。
本文将从苝酰亚胺自由基的定义、合成方法、反应特点以及应用领域等方面进行介绍。
苝酰亚胺自由基是指分子中含有苝酰亚胺基团（R-C=NR'）的自由基。
它的结构中有一个未成对电子，使其具有较高的反应活性。
苝酰亚胺自由基可以通过多种途径合成，其中最常用的方法是通过氧化反应获得。
例如，苯基苝酰胺可以通过过氧化苯基苝酰胺的热解来得到苝酰亚胺自由基。
苝酰亚胺自由基具有很强的反应活性，可以参与多种有机反应。
首先，它可以与另一个自由基发生反应，形成新的化学键。
这种反应被广泛应用于有机合成中，例如在氢转移反应中，苝酰亚胺自由基可以与醇类反应，形成醛或酮。
此外，苝酰亚胺自由基还可以参与自由基聚合反应，如自由基聚合聚合物的合成。
苝酰亚胺自由基还具有其他一些特殊的反应特点。
例如，它可以参与自由基加成反应，与烯烃或炔烃反应，形成新的C-C键。
此外，苝酰亚胺自由基还可以参与氧化反应，与氧气或氧化剂反应，生成相应的氧化产物。
苝酰亚胺自由基在有机合成领域具有广泛的应用价值。
首先，由于其反应活性高，它可以作为反应介质或催化剂参与多种重要的有机转化反应。
其次，苝酰亚胺自由基还可以用于有机合成中的碳-碳键构建。
此外，苝酰亚胺自由基还可以用于有机电化学反应、光化学反应以及自由基聚合反应等领域。
苝酰亚胺自由基是一种重要的有机中间体，具有广泛的应用价值。
它的合成方法多样，反应特点独特，可以参与多种有机反应。
在有机合成领域，苝酰亚胺自由基被广泛应用于催化剂、反应介质以及碳-碳键构建等方面。
随着有机化学领域的不断发展，相信苝酰亚胺自由基将发挥更加重要的作用，为有机化学合成提供更多的可能性。
新型苝酰亚胺衍生物的合成及其光学性能_杜斌
到限制。 为了改善 Ⅰ 的溶解度， 必须对其进行修 饰。针对 Ⅰ 的修饰主要集中于两个位置： 一是在
*
0326 收稿日期： 2012基金项目： 国家重点基础研究发展计划（ 973 ） 资助项目（ 2011CB706902 ） 作者简介： 杜斌（ 1987 － ） ， 男， 汉族， 山东济宁人， 硕士研究生， 主要从事军事化学与烟火技术的研究。 mail： fhyjy404@ 163． com 通信联系人： 余建华， 研究员， 博士生导师，E-
1 Vis 和荧光光谱研究了他们的光学性质 。 结构经 H NMR 和 MS 表征。用 UV-
关
键
词： 苝四酸二酐； 苝酰亚胺； 合成； 光学性质 文献标识码： A 1511 （ 2012 ） 04042104 文章编号： 1005-
中图分类号： O625
Synthesis and Optical Properties of Novel Perylene Diimide Derivatives
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苝酰亚胺
Liquid Crystalline Perylene Diimide Outperforming Nonliquid Crystalline Counterpart:Higher Power Conversion Efficiencies(PCEs) in Bulk Heterojunction(BHJ)Cells and Higher Electron Mobility in Space Charge Limited Current(SCLC)DevicesYoudi Zhang,†Helin Wang,†Yi Xiao,*,†Ligang Wang,‡Dequan Shi,‡and Chuanhui Cheng*,‡†State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian116024,People’s Republic of China‡School of Physical and Optoelectronic Engineering,Dalian University of Technology,Dalian116024,People’s Republic of China *Supporting Informationoptimized efficiency of0.94%.By contrast,the devices based on PDI-1,afficiency of0.22%.Atomic force microscopy(AFM)images confirmordered morphology.In space charge limited current(SCLC)deviceselectron mobility of2.85×10−4cm2/(V s)(at0.3MV/cm)which issame conditions for thermal annealing at120°C.semiconductor,perylene diimides,liquid crystalline,space charge limited current1.INTRODUCTIONIn recent years,liquid crystalline(LC)semiconductors have received considerable attention in thefields of organicelectronics.1−4Not only because they are readily dissolvable,butalso because they self-assemble into highly ordered morphology5 to effectively eliminate the structural and electronic defects.6,7LCmaterials are highly desirable for solution-processable devices.8It isnot surprising that some space charge limited current(SCLC) devices and organicfield-effect transistors(OFET)devices basedon LC semiconductors have shown very high charge mobility.9−13 However,in thefield of bulk heterojunction(BHJ)organic solar cells,the applicability of LC materials have not been well-recognized.14Actually,amorphous fullerenes derivatives,e.g.,PCBM,firmly occupy the dominant status as electron acceptors in BHJ cells,although have poor absorption in solar spectrum. Generally speaking,there is still a wide gap between non-fullerene organic acceptors and fullerenes in terms of BHJ efficiency.Among all the reported nonfullerene acceptors,one representative class is perylene diimides(PDIs),which have very strong absorption in the visible region and exhibit high electron mobility.However,because of their large,rigid,and planar conjugation cores,the seriousπ−πstacking and poor solubility of the PDIs and their analogues are problematic for BHJ cells;they tend to aggregate excessively to form islets,which not only damages the morphology of the BHJ active films but also generates carrier traps.A variety of strategies have been put forward to reduce the extent ofπ−πstacking,improve solubility,and control the aggregation state.15These working concepts include the introduction of swallow tail-type long, branchy,andflexible alkyl side chains onto the two imide sites,16−18copolymerization of PDI and other conjugated monomer on the perylene bay sites,19direct connection of two PDI segments on the imide site to form nonplanar and nonconjugate dimers,20and combination of PDI and donor on the imide site to form co-oligomers,21etc.Herein,we propose the utilization of liquid crystalline PDI derivatives,e.g.,LC-1,as a new means parallel to the above-mentioned ones helping to improve the applicability of PDIs in BHJ cells.In this work,LC-1,which is a structurely simple PDI derivative acting as the model of our strategy,has been adopted as the acceptor in the fabrication of BHJ cells’active layers with P3HT as the donor.Devices based on LC-1exhibit remarkably higher conversion efficiency than the nonliquid crystalline counterpart PDI-1.15To better understand the reason whyReceived:August9,2013Accepted:October15,2013Published:October15,2013LC-1is in favor of BHJ solar cells,its LC properities have been thoroughly characterized by di fferential scanning calorimetry (DSC),polarization optical microscopy (POM),and X-ray di ffraction (XRD);In addition,in spin-coated SCLC devices,LC-1’s intrinsic electron mobility is much higher than that of PDI-1.2.RESULTS AND DISCUSSION2.1.Fundamental Characteristics of LC-1Material.LC-1molecule was designed and synthesized according to a previous procedure,22as shown in Scheme 1.Solubility of LC-1was 40mg/mL in the common organic solution, e.g.,dichloromethane,chloroform,chlorobenzene,and dichloro-benzene,and it was very important for applied in BHJ solar cells.IN addition,the absorption spectra of LC-1do not have to change for modi fication of PDI N-terminal chains at 527nm in the solution and at 495nm in the film (see Figure 1).Thethermogravimetric analysis (TGA)curve showed the enhanced thermal stability for LC-1with a decomposition onset temperature (T d )of ∼333.7°C (see Figure 2).2.2.Photovoltaic Device Performance.In the compar-ison investigation on BHJ devices using liquid crystalline LC-1and n PDI-1,respectively,as acceptor materials,cells based on LC-1exhibited remarkably superior performances.For the device with P3HT:LC-1as an photovoltaic active layer,the optimum power conversion e fficiency (PCE)was 0.94%,which is ∼4times that of a device based on the P3HT:PDI-1(maximum PCE of 0.22%).These data supported our hypothesis that liquid crystalline acceptor materials are more advantageous in BHJ solar cells.Interestingly,there exists the regularity in the high dependence of devices ’s performances on the annealing temperature,which is related to the broad temperature range of LC-1’s liquid crystalline phase.Keeping the P3HT:LC-1weight ratio fixed at 1:2in the active layer,and setting a series annealing temperature (50,80,100,120,150,and 165°C),we tested the J −V curves of a group of BHJ devices (100mW cm −2AM 1.5G),as recorded in Figure 3,and we summarized the corresponding data in Table 1.Particularly,the correlation between annealing temperature and PCE and the correlation between annealing temperature and short-circuit current (J SC )had been clearly demonstrated in Figure 4.With the increase in annealing temperature from 50°C to 120°C,the continuous and obvious enhancements in device parameters including J SC ,open-circuit voltage (V OC ),and fill factor (FF)were found.The increased J SC may result from a reorientation and enhanced ordering of the LC-1during annealing,which would facilitate charge transport.However,at >120°C,further increases in the annealing temperature induced a decrease in device performance.Thus,using thermal annealing at 120°C resulted in the best data:PCE =0.94%,V OC =0.41V,J SC =5.42mA cm −2,and FF =0.42.In the control experiment,the BHJ device unannealed at 25°C only showed a much lower PCE of 0.23%,which is only a quarter of the optimum e fficiency.When we changed the P3HT:LC-1blended ratio into 1:1,the similar regularity on the e ffects of annealing temperature toScheme 1.Synthetic Routes of the Investigated LC-1MoleculeFigure 1.Normalized absorption spectra of (■)LC-1chloroform solution (1×10−5),(○)LC-1film,and (●)P3HT:LC-1blended film.Figure 2.TGA thermograms of liquid crystalline molecule LC-1measured under nitrogen flow (50mL min −1)at a heating rate of 10°C min −1.Figure 3.Current −voltage (J −V )curves of photovoltaic devices using P3HT:LC-1as active layers at temperatures of 25and 120°C and weight ratios of 1:1and 1:2,respectively.The curves correspond to the curve of P3HT:LC-1using (□)a weight ratio of 1:1at 25°C,(■)a weight ratio of 1:1at 120°C,(○)a weight ratio of 1:2at 25°C,and (●)a weight ratio of 1:2at 120°C.device data had also been observed;Again,the best performance (PCE =0.74%,V OC =0.38V,J SC =5.03mA cm −2,and FF of 0.39)was obtained under the condition of thermal annealing at 120°C.However,in the BHJ devices using the nonliquid crystalline PDI-1as the acceptor,thermal annealing did not seem to be as bene ficial as it did to LC-1.After annealing at 120°C,a device of P3HT:PDI-1(1:1)showed a J SC value of 1.6mA cm −2,V OC =0.34V,FF =0.40,and an e fficiency of 0.22%.These data were much lower than those obtained from the P3HT:LC-1device annealing at 120°C,but were similar to those of the unannealed P3HT:LC-1device.The above facts indicated that the improvement induced by thermal annealing was more related to LC-1’s liquid crystalline feature than to the perylene diimide conjugation core.To better understand the e ffects of the P3HT:LC-1weight ratio to photovoltaic performances,the comparisons of di fferent parameters (e.g.,external quantum e fficiencies (EQE)and internal quantum e fficiencies (IQE))were carried out.As shown in Figure 5A,the highest EQE (∼17%)was obtained for the blends of 1:2at 490nm,while for P3HT:LC-1(1:1)devices,the highest EQE value is just ∼13%at 485nm,the tested result implied that the increased proportion of LC-1molecule produced more photocurrent in the blended films and also veri fied the improved J SC observed in LC-1devices,which showed higher EQE values (peak EQE =17%)over the entire range of the active layer absorption from 350nm to 700nm,a signi ficant portion of that photocurrent is due to absorption by the acceptor phase,followed by hole transfer to the donor.As shown in Figure 5B,the IQE tests also suggested that much more charge carriers were generated for P3HT:LC-1(1:2)(∼22%)under sunlight,compared with that of the doping ratio of 1:1(∼16%).2.3.Atomic Force Microscopy Images.Atomic force microscopy (AFM)images revealed that the active layer morphology of P3HT:LC-1were greatly in fluenced by their weight ratios and the thermal annealing.As shown in Figure 6,a P3HT:LC-1ratio of 1:2produced much smoother morphology than ratio of 1:1;Also,the morphology after thermal annealing at 120°C was much smoother than that unannealed at 25°C.The root-mean-square (RMS)surface roughness values could be the indicators for the quality of films:the smaller the RMS surface roughness,the better the film morphology.On one hand,the smallest RMS surface roughness of 4.67nm for a doping ratio of 1:2under the thermal annealing at 120°C had been determined;this value was smaller than 5.50nm,which corresponds to the film without annealing.On the other hand,for the unannealed film with a doping ratio of 1:1,the RMS surface roughness value was 7.61nm,but after annealing at 120°C,the value decreased toTable 1.Performance of the Devices with Di fferent Weight Ratios and Thermal Annealing Conditions of P3HT:LC-1from o -Dichlorobenzene Solution Used for Spin Coatingtemperature [°C]PCE [%]J SC [mA cm −2]V OC [V]FF P3HT:LC-1Weight Ratio =1:1250.16 1.770.350.26500.43 3.580.360.33800.55 4.250.360.361000.65 4.330.400.381200.74 5.030.380.391500.67 4.310.410.381650.50 3.200.390.40P3HT:LC-1Weight Ratio =1:2250.23 1.880.360.34500.64 4.160.380.40800.71 4.670.370.411000.86 4.890.400.441200.94 5.420.410.421500.77 4.650.440.38P3HT:PDI-1Weight Ratio =1:1a1650.61 4.220.390.371200.22 1.600.340.40aThe mixing solution of P3HT:PDI-1was used as an organicphotovoltaic activelayer.Figure 4.Relationship chart of PCE and J SC versus temperature to P3HT:LC-1at di fferent temperatures and weightratios.Figure 5.(A)External quantum e fficiencies (EQE)and (B)internal quantum e fficiencies (IQE)of P3HT:LC-1at di fferent weight ratios.6.40nm.The decrease in the roughness of the blend films after annealing was due to the fact that the LC-1molecules were self-organized into ordered structures at 120°C within the liquid crystalline phase.The phenomenon that the increase in the proportion of LC-1in the blended film can improve morphology should also be ascribed to liquid crystalline characteristics.Because of the nonliquid crystalline feature of PDI-1,the morphology of the P3HT:PDI-1films would not be improved by the thermal annealing;the RMS surface roughness was high,up to 9.29nm,even after annealing at 120°C.Since the smooth morphology leaded to an e fficient charge separation,higher J SC and PCE for BHJ PV devices based on the thermally annealed blend films of P3HT:LC-1than those of P3HT:PDI-1can be partially explained.2.4.Charge Mobility.Charge mobility within an active layer film is another critical factor for BHJ cells.Since we had already found that,in P3HT:LC-1BHJ devices,thermal annealing greatly improved the PCE,for the sake of deeper interpretation of such e ffect,it would be useful to evaluate LC-1’s electron mobility at di fferent annealing temperature.Hence,we adopted the space charge limited current (SCLC)method,12,23−26which is suitable for determining organic semiconductors ’intrinsic carrier mobility under steady-state current.Consistent with the former P3HT:LC-1bulk hetero-junction solar cells device structure,the SCLC devices ’structure was designed to be ITO/ZnO (∼30nm)/LC-1(∼250nm)/LiF (1.5nm)/Al (100nm).J −V curves of the SCLC devices with spin-coated LC-1as the active layer annealed at di fferent temperatures were recorded (Figure 7),and the correspondingparameters have been collected in Table 2.The SCLC in this case of mobility,depending on the field,can be approximated by the following formula:27,28εεμγ=J E LE 98exp (0.89)020where E is the electric field across the sample;εand ε0are the relative dielectric constant and the permittivity of the free space,respectively;and L is the thickness of the organic layer,with μ0the zero-field mobility and γdescribing the field activation of the mobility.With the increase in annealing temperature,the electron mobility of LC-1first increased sharply,e.g.,from 4.90×10−6cm 2/(V s)at 25°C to 1.72×10−5cm 2/(V s)(at 0.3MV/cm)at 50°C;such a tendency of increase ceased at 120°C,where the electron mobility achieved the highest value,2.85×10−4cm 2/(V s),which is 50times higher than that of the unannealed device (25°C);Then,further temperature elevation would result in an apparent decrease in electron mobility,e.g.,to 2.93×10−5cm 2/(V s)at 150°C.Amazingly,such a correlation between the electron mobility of LC-1and annealing temperature exhibited the same regularity as that of the PCE of P3HT:LC-1BHJ solar cells.Hence,the best PCE of BHJ solar cells at 120°C can be reasoned by the highest electron mobility of LC-1at this temperature.29,30The SCLC device using the nonliquid crystalline PDI-1had also been tested.However,even if PDI-1film had undergone the thermal annealing at 120°C,the SCLC electron mobility was determined to be 5.83×10−5cm 2/(V s),which is only one quarter of that of LC-1.This fact could be used to explain why BHJ cells using LC-1as an acceptor outperformed those using PDI-1.In BHJ organic solar cells,the balanced charge carrier mobilities reveal that LC-1increases the FF and PCE,because of charge separation.31,32To investigate the carrier mobilities (electron and hole)in the blend films,the J −V characteristics of the hole-only (ITO/PEDOT:PSS/LC-1or PDI-1:P3HT/Au structure)and electron-only (Al/LC-1or PDI-1:P3HT/LiF/Al structure)devices were measured for the as-cast and annealed blended films (see Tables 3and 4).The hole and electron mobilities were extracted using the SCLC model 33,34(Figure 8).For the annealed blended film at 120°C,the values of the hole and electron mobilities are ∼1.07×10−6and ∼1.28×10−5cm 2/(V s),respectively.However,the hole and electron mobilities fortheFigure 6.AFM height images (5μm ×5μm)of blended thin films of P3HT:LC-1before thermal annealing (A)at 25°C,P3HT:LC-1=1:1;(B)at 120°C,P3HT:LC-1=1:1;(C)at 25°C,P3HT:LC-1=1:2)and after thermal annealing ((D)at 120°C,P3HT:LC-1=1:2;and (E)at 120°C,P3HT:PDI-1=1:1).Figure 7.Current density versus voltage (J −V )characteristics of anelectron-only device based on (●)LC-1at 25°C,(○)LC-1at 120°C,(■)LC-1at 165°C,and (□)PDI-1at 120°C at an electric field strength of 0.3MV/cm.Table 2.Performance of the Single Electron Devices LC-1with Di fferent Thermal Annealing Conditions fromChloroform Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μ[cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-125 4.90×10−61.16×10−70.006850 1.72×10−57.81×10−60.0014802.91×10−5 1.05×10−50.00181003.92×10−5 1.02×10−60.0066120 2.85×10−4 1.92×10−50.0049150 2.93×10−5 3.95×10−70.0078165 1.74×10−55.37×10−60.0021PDI-1a1205.83×10−5 4.35×10−70.0089aThe single electron device based on PDI-1from chloroform solution used for spin coating at an electric field of 0.3MV/cm.as-cast blend are ∼1.07×10‑7and 8.20×10−8cm 2/(V s),respectively.As the annealing temperature increases up to 120°C,the hole mobility and electron mobility increase,which can be attributed to the improvement of film morphology and,thereby,is the reason for the higher PCE.However,the hole mobility and electron mobility of the PDI-1:P3HT film are 5.52×10−5and 4.58×10−7cm 2/(V s)at 120°C,respectively.Obviously,the strong aggregation tendency of nonliquid crystalline PDI-1can result in more charge recombination and unbalanced charge transport in the blend films,which explains the lower performance of PDI-1:P3HT BHJ devices.Since the investigations of all of the above devices had indicated that the annealing temperature played a decisive role in improving the PCE,mobility,and morphology,thoroughly investigating the thermal properties of LC-1should be carried out to provide deeper insight into the correlation between the liquid crystalline phase and the suitable annealing temperature.2.5.Di fferential Scanning Calorimetry (DSC),Polar-ization Optical Microscopy (POM),and X-ray Di ffraction (XRD).As shown in Figure 9,the DSC heating curve of LC-1showed two reversible transitions:at 54°C and 172°C.The corresponding transitions upon cooling were observed at 158°C and 41°C.Such information indicated a broad liquid crystalline phase (∼112°C),which was conductive to optimizing the annealed temperature for organic photovoltaic devices.The P3HT:LC-1BHJ devices that underwent annealing at 120°C generated a highest PCE,possibly because this annealing temperature was in the upper section of the liquid crystalline phase.POM (see Figure 10)experiments upon cooling from the isotropic melt gave evidence for a highly ordered mesophase which is a typical characteristics for the liquid crystalline materials.22,35−37Figure 10A at 120°C showed that the entire glass substrate covered a very compact and uniform film composed of small snow flake-like textures,in contrast to Figure 10B at 165°C with the larger and inhomogenous islets.The results implied that thermal annealing at di fferent temperature would in fluence the particle size and uniformity in the mesophases to di fferent extents and,thus,a ffect the electron mobility 38and PCE.So,there was no wonder that annealing atTable 3.Electron Mobilities of LC-1:P3HT with Di fferent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μe [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 258.20×10−87.76×10‑90.004350 2.33×10−6 1.24×10−70.005380 3.33×10−6 1.36×10−70.00581009.42×10−6 4.43×10−70.0056120 1.28×10−5 1.44×10−60.0040150 3.34×10−6 3.10×10−80.0085165 1.96×10−72.33×10−80.0081PDI-1:P3HT a 1204.58×10−73.89×10−90.0087aThe electron mobility based on PDI-1:P3HT blended film from o -dichlorobenzene solution used for spin coating at an electric field of 0.3MV/cm.Table 4.Hole Mobilities of LC-1:P3HT with Di fferent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μh [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 25 1.07×10−79.32×10−90.004450 2.70×10−7 4.02×10−80.003580 3.97×10−7 4.94×10−80.00391009.12×10−7 4.85×10−70.0011120 1.07×10−6 2.21×10−70.0029150 5.83×10−7 2.49×10−80.0057165 3.20×10−75.08×10−80.0033PDI-1:P3HT a 1205.52×10−52.18×10−70.0101aThe hole-only mobility based on PDI-1:P3HT blended film from o -dichlorobenzene solution used for spin coating at an electric field of 0.3MV/cm.Figure 8.Current density versus voltage (J −V )characteristics of (A)electron-only devices and (B)hole-only devices based on (◇)LC-1:P3HT at 25°C,(■)LC-1:P3HT at 120°C,(□)LC-1:P3HT at 165°C,and (◆)PDI-1at an electric field strength of 0.3MV/cm.Figure 9.Di fferential scanning calorimetry (DSC)traces of LC-1at a ramp rate of 10°C/min.120°C resulted in highest electron mobility of LC-1and the best performance in BHJ solar cells.Also,XRD experiments were in accordance with a columnar smectic ordering of the mesogens.The di ffractogram of LC-1from 25°C to 165°C are shown in Figure 11.The di ffractionpeaks of the 25°C sqample showed a relatively weak and wide single peak at 2θ=2.55°(corresponding to 34.61Å).However,upon further heating LC-1into a liquid crystalline phase,a strong and narrow di ffraction peak at 2θ=2.14°(41.23Å)and 2θ=25.85°(3.44Å)appeared and became more and more sharp as the temperature increased.The re flection at 25.85°in the wide-angle regime depicts a moderate intracolumnar long-range order with a π−πstacking distance of d ππ=3.44Å.LC-1crystalline at 165°C was the best and was much better than that at 25°C.Meanwhile,we found that,at higher temperature,the overall di ffraction peaks move slightly toward the direction of the small-angle di ffraction.While new di ffraction peaks at 2θ=9.2°,15.1°,and 17.8°emerged at higher temperature,the original peak with 2θ=21.1°in the 25°C di ffractogram disappeared in the wide-angle regime.These changes re flected that,in the liquid crystalline phase,LC-1has a highly ordered columnar smectic phase,which is similar to the results of Jin,who had studied a series of LC PDI derivatives containing amino-acids eater and found they have the parallel stacking forms in LC phase.XRD di ffraction patterns of the blended LC-1:P3HT (2:1)films reveal that thermal annealing is critical for the films ’crystallinity,as shown in Figure 12.The best annealing temperature is 120°C,which results in sharper and stronger peaks at 2θ= 2.43°and 4.66°than other temperatures.Although these two 2θpeaks are the distinct packing characteristics of all the perylenediimides,they do not appear in the XRD patterns of the films annealed at lowertemperatures (25,80,and 100°C).Thus,the side chains of LC-1endue this PDI derivative a reasonable self-tunability in packing behavior.While P3HT shows only very weak and broad di ffraction peaks,indicating quite disordered donor phases,the highly ordered arrangement in the blend film annealed at 120°C can only be attributed to liquid crystalline phase of LC-1.The above XRD results of the blended films are identical to that of the pure LC-1,which again con firms that thermal annealing at a higher temperature within liquid crystalline phase will produce optimum PCE in BHJ organic solar cells.3.CONCLUSIONIn summary,we have developed and characterized a liquid crystalline perylene diimide acceptor LC-1.It exhibited a liquid crystalline phase with a broad temperature range from 41°C to 158°C,which is essential for optimizing the thermal annealing to improve the morphology of organic films,charge mobility,and device e fficiency.The LC properties of LC-1have been thoroughly investigated by DSC,POM,and XRD.During device investigation,it is found that 120°C is the best temperature for thermal annealing,which results in the highest electron mobility in SCLC devices and highest PCE in BHJ solar cells.This temperature is in the upper part of the LC phase,at which LC-1forms highly ordered films with compact and uniform crystalline particles.The BHJ devices,using P3HT:LC-1(1:2)as organic photovoltaic active layer under-going thermal annealing at 120°C,shows an optimized e fficiency of 0.94%.In contrast,the devices based on PDI-1,which is a nonliquid crystalline PDI counterpart,only obtain a much lower e fficiency of 0.22%.Atomic force microscopy (AFM)images con firm that the active layers composed of P3HT:LC-1have smooth and ordered morphology.In SCLC devices fabricated via the spin-coating technique,LC-1shows the intrinsic electron mobility of 2.85×10−4cm 2/(V s),which is almost 5times that of the PDI-1value (5.83×10−5cm 2/(V s))under the same conditions for thermal annealing at 120°C.Because of the broad temperature range of the liquid crystalline phase of LC-1,thermal annealing at higher temperatures will result in mild aggregation and thus,improve the order and morphology of the LC-1:P3HT blended films,which is favorable for the balanced electron and hole transport and thereby higher PCE.However,when using nonliquid crystalline PDI-1as an acceptor,its strong aggregation results in poor exciton dissociation and charge transport of the blend films.Figure 10.Polarizing optical microscopy (POM)images of LC-1(under crossed polarizers)at (A)120°C and (B)165°C.Figure 11.X-ray di ffraction (XRD)patterns of LC-1at 25,80,100,120,150,and 165°C.Figure 12.XRD patterns of LC-1:P3HT (2:1)blended films from o -dichlorobenzene solution used for spin coating on ITO/PEDOT:PSS substrate.In addition,the blend films are measured at room temperature (RT)without annealing and after annealing at 80,100,120,150,and 165°C.Thus,LC-1is more competent than PDI-1.This concept of utilizing liquid crystalline perylene diimide is worth extending to other types of non-fullerene organic semiconductors in order to discover more e fficient alternatives to PCBM and further improve the performances of BHJ solar cells.4.EXPERIMENTAL SECTIONSynthesis of LC-1.N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-peryle-netetracarboxyldiimide and LC-1was synthesized according to procedures reported by Jin ’s group.22N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-perylenetetracarboxyldiimide (6.95g,12.99mmol)was dissolved in an aqueous solution of 5%NaHCO 3(100mL).ALIQUAT 336(9.6g,ca.20mmol)was dissolved in a 2:1(v/v)ethanol/water mixture (120mL).The two solutions were mixed and stirred at room temperature for 30min.The mixture was then extracted three times with petroleum ether (500mL),and the combined petroleum ether solution was evaporated to dryness.The residue was further dried at 75°C for 2h in a vacuum oven and then dissolved in dimethylformamide (DMF)(100mL).1-Bromooctade-cane (9.54g,28.6mmol)was added and the mixture was stirred at room temperature for 12h.The mixture was then poured into methanol (400mL).The product was collected as an orange powder via suction filtration and washed thoroughly with methanol.After drying,the product LC-1at 75°C in a vacuum oven to constant weight,it was puri fied by column chromatography on silica gel using 4:1(v/v)CH 2Cl 2/n -hexane as the eluent.Yield:10.50g (78%).1H NMR (400MHz,CDCl 3,δ)8.58(d,2H),8.43(t,2H),5.79(m,1H),4.29−4.10(m,2H),1.82−1.54(m,5H),1.19(d,30H),0.87(t,3H);13C NMR (100MHz,CDCl 3,δ)170.44,162.73,134.69,131.76,129.47,126.38,123.22,65.89,49.77,32.10,29.86,29.71,29.54,29.38,28.66,26.10,22.87,14.98,14.30;HRMS (MALDI-TOF,m/z):[M +Na]+calcd for C 66H 90N 2O 8Na,1061.6595;found,1061.6569.1H and 13C NMR spectra of the final product,LC-1,are provided in the Supporting Information.Materials Characterization.1H and 13C NMR spectra were recorded using a 400MHz Bruker in CDCl 3at 293K using TMS as a reference.Accurate mass correction was measured with MALDI ToF mass spectrometer (MALDI micro MX).Thermogravimetric analysis (TGA)were carried out using a Mettler −Toledo TGA/SDTA 851e at a heating rate of 10°C min −1under nitrogen flow of 20mL min −1.Di fferential scanning calorimetry (DSC)analyses were performed on a DSC Q100(TA Instruments).DSC curves were recorded at a scanning rate of 10°C min −1under nitrogen flow.Phase transitions were also examined using a POM Nikon Diaphot 300with a Mettler FP 90temperature-controlled hot stage.X-ray di ffraction (XRD)measurements were performed on a Bruker D8Avance equipped with a Huber quartz monochromator 611with Cu K α1=1.54051Å.Film thicknesses were determined on an Alphastep 500surface pro filometer.UV-vis absorption spectra in chloroform (CHCl 3)solution were recorded in a UV-vis spectrophotometer (Model HP8453)at room temperature using a glass cuvette with a path length of 1cm.Device Preparation and Characterization.BHJ organic device preparation proceeds as follows.A 15Ωcm −2resistor of indium-doped tin oxide (ITO)substrate was purchased from Xiangcheng Science and Technology Co.,Ltd.,and then the substrates underwent a cleaned course in an ultrasonic bath with acetone,ethanol,and ultrapure water and dried for 1h under a blast dry oven.Subsequently,the glasses were cleaned in oxygen plasma treatment for 10min,and a PEDOT:PSS (Clevios P VP AI 4083,H.C.Starck)solution was then spin-coated at 2000rpm for 60s onto the cleaned ITO surface,resulting in a thickness of ∼40nm,as determined with a Dektak surface pro filometer.The PEDOT:PSS layer was annealed for 30min at 120°C in air.A solution of active layer P3HT (Rieke No.4002-E)and LC-1were simultaneously dissolved in dichlorobenzene in a weight ratio of 1:1at a concentration of 15mg mL −1and stirred for 1h at a temperature of 90°C in an oil bath.Before deposition of the active layer,the mixed solution of P3HT:LC-1was filtered through a polytetra fluoroethylene(PTFE)syringe filter (0.45μm pore size).The active layer was then spin-coated on top of the PEDOT:PSS film at 600rpm (dichlorobenzene)for 18s resulting in a film thickness of ∼96nm.Aluminum counter electrodes were evaporated through a shadow mask on top of the active layer with a thickness of ∼100nm.The films were annealed at 120°C for 30min in the vacuum state.The active area of the pixels,as de fined by the overlap of anode and cathode area,was 12mm 2.The photovoltaic performance was determined under simulated sunlight,using a commercial solar simulator (Zolix ss150solar simulator,China).Device Characterization.The external quantum e fficiency (EQE)characterization of all devices was performed in air.The light output from a xenon lamp was monochromated by a Digichrom Model 240monochromator,and the short-circuit device photocurrent was monitored by a Keithley electrometer as the monochromator was scanned.A calibrated silicon photodiode (818-UV Newport)was used as a reference in order to determine the intensity of the light incident on the device,allowing the EQE spectrum to be deduced.■ASSOCIATED CONTENT*Supporting Information 1H and 13C NMR spectra of LC-1.Thermal gravimetric analysis (TGA)of LC-1.UV-vis absorption spectra of LC-1in chloroform (CHCl 3)solution and the film.This material is available free of charge via the Internet at .■AUTHOR INFORMATIONCorresponding Authors*E-mail:xiaoyi@.*E-mail:chengchuanhui@.Author ContributionsThe manuscript was written through contributions of all authors.All authors have given approval to the final version of the manuscript.NotesThe authors declare no competing financial interest.■ACKNOWLEDGMENTSThis work was supported by National Natural Science Foundation of China (No.21174022),National Basic Research Program of China (No.2013CB733702)and Specialized Research Fund for the Doctoral Program of Higher Education (No.20110041110009).■REFERENCES(1)Li,Q.,Ed.Self-Organized Organic Semiconductors:From Materials to Device Applications ;John Wiley &Sons:Hoboken,NJ,2011.(2)Li,Q.,Ed.Liquid Crystals Beyond Displays:Chemistry,Physics,and Applications ;John Wiley &Sons:Hoboken,NJ,2012.(3)Li,L.;Kang,S.W.;Harden,J.;Sun,Q.;Zhou,X.;Dai,L.;Jakli,A.;Kumar,S.;Li,Q.Liq.Cryst.2008,35,233−239.(4)Zhou,X.;Kang,S.-W.;Kumar,S.;Li,Q.Liq.Cryst.2009,3,269−274.(5)Zhou,X.;Kang,S.-W.;Kumar,S.;Kulkarni,R.R.;Cheng,S.Z.D.;Li,Q.Chem.Mater.2008,20,3551−3553.(6)Fitzner,R.;Elschner,C.;Weil,M.;Uhrich,C.;Koerner,C.;Riede,M.;Leo,K.;Pfeiffer,M.;Reinold, E.;Mena-Osteritz, E.;Baeuerle,P.Adv.Mater.2012,24,675−680.(7)Schrader,M.;Fitzner,R.;Hein,M.;Elschner,C.;Baumeier,B.;Leo,K.;Riede,M.;Baeuerle,P.;Andrienko,D.J.Am.Chem.Soc.2012,134,6052−6056.(8)Sun,Q.;Dai,L.;Zhou,X.;Li,L.;Li,Q.Appl.Phys.Lett.2007,91,253505/1−253505/3.(9)Struijk,C.W.;Sieval,A.B.;Dakhorst,J.E.J.;van Dijk,M.;Kimkes,P.;Koehorst,R.B.M.;Donker,H.;Schaafsma,T.J.;Picken,。
偶氮基团修饰的苝酰亚胺染料的合成及其光响应行为
ｌ 实 验 部 分
１ ． １ 仪 器 与 试 剂
基 金 项 目 ：国 家 自 然 科 学 基 金 （ ５ ０ ５ ７ ３ ０ １ ９ ／ ５ １ ２ ７ ３ ０ ６ １ ） ； 教 育
第４ Ｏ卷 第 ４期
北 京 化 工 大 学 学报 （自然 科 学 版 ）
Ｊ ｏ ｕ ｒ ｎ ａ ｌ ｏ ｆ Ｂ ｅ ｉ ｊ ｉ ｎ ｇ Ｕｎ ｉ ｖ ｅ ｒ ｓ ｉ ｔ ｙ ｏ ｆ Ｃ ｈ ｅ ｍｉ ｃ ａ ｌ Ｔ ｅ ｃ ｈ ｎ ｏ ｌ ｏ ｇ ｙ（ Ｎａ ｔ ｕ ｒ ａ ｌ Ｓ ｃ ｉ ｅ ｎ ｃ ｅ ）
了巨大 的应 用前 景 ¨ 。 酰亚胺 类化 合 物 具有 大
的 一 订共 轭 电子 体系 结构 ， 是 一 类 性 能优 异 的 ｎ型 半 导体 材料 ， 已广泛 应用 于有 机 电致 发 光二极 管 、 太 阳能 电池 、 场效应 晶体 管 和 分 子 器 件 等 高新 技 术 领 域 Ｊ 。将 偶 氮生 色 团和 茈 酰亚 胺 从 不 同角 度 ， 通 过 不 同方 式 实现 两者 功 能 特 性 的 互补 、 重组 和集 成 已 引起研 究人 员 的关 注 ， 如Ｆ ｅ ｎ ｇ等 。 。 将 Ｎ一 十 二烷 基 一 茈． ３ ， ４ － 甲酸 酐－ ９ ， １ ０ 一 亚胺 与 １ ， ４ － 二 氨 基 偶 氮 苯 缩 合， 得 到一 种 Ｎ 一 十二烷基． Ｎ 一 偶 氮 基 团取 代 的不 对 称茈 酰亚 胺 化 合 物 ， 由于分 子间 强的 盯 一 盯堆 积 作
中 图 分 类 号 ：０ ６ ４ １
引 言
偶 氮苯 生 色 团 具有 一 种 特 殊 的光 响 应 性 能 ， 在 光 照激 发下 吸收 光 能会 产 生 可 逆 的顺 反 异 构 ， 且 在
苝酰亚胺类物质的研究进展
苝酰亚胺类物质的研究进展⼀：苝酰亚胺的研究进展3.1.1 ⽔溶性的苝酰亚胺类物质的研究进展从Kardos在1913年合成第⼀个苝系衍⽣物以来,⼈们开始对苝系衍⽣物的合成进⾏了多⽅⾯的探讨。
⼤多数苝酰亚胺化合物以其难溶性⽽著称，对于如何提⾼苝⼆酰胺的溶解性，⼀直是研究的热点之⼀。
对于如何提⾼苝⼆酰胺的溶解性研究者们⼀般采取两种⽅式解决，其⼀是Langhals教授提出，在酰亚胺的氮原⼦上引⼊增溶性的基团，这样得到的分⼦在吸收和发射特征上没有明显的分别，这是由于酰亚胺基团的氮原⼦上产⽣的HOMO 和LUMO轨道的节点（node）减弱了苝核同与氮相连的取代基的耦合作⽤。
其⼆就是BASF公司的Seybold教授⾸次提出的在海湾处（bay-area）引⼊取代基，即在苝四羧酸⼆酐和苝四羧酸⼆酰亚胺的1,7或1,6,7,12位上引⼊增溶性取代基团。
2003年，D.Y.Yan等⼈将低聚的分⼦与苝核连接在⼀起，得到了溶解性良好的关于苝系的聚合物。
2006年，H.Tian等⼈⼜将与苝相连的聚合物链的长度加长，得到了溶解性更好，光电性质良好的苝系衍⽣物进⽽可以应⽤于太阳能电池领域。
2008年Y.J.Shen等⼈⼜将含硫原⼦的杂环长链接在了酰亚胺的位置，同样得到了溶解性、电化学性质都良好的有机多功能分⼦。
2009年，S.Icli等⼈⼜将上述苝系衍⽣物的燕尾形的扩展为⽤氮连接的长的脂肪链，同样的增加了苝系衍⽣物的溶解性，并研究了它们的光物理性质和电化学性质，进⼀步扩⼤了苝系衍⽣物的数量。
2007年P.A.Troshin等⼈将苝酐⽔解变成羧酸盐进⽽变为酯，同样可以改善此类化合物的溶解性，这种化合物的光物理性质和电化学性质使其成为有机光转换材料。
2009年H.Z.Chen等⼈⼜将苝酐的⼀侧做成酰亚胺的形式，另⼀侧⽔解成酯的形式，同样使得化合物具有良好溶解性。
⼆：苝酰亚胺类物质的应⽤难点、热点以及前景举例3.2.1苝酰亚胺类物质的研究热点苝酰亚胺类化合物作为⼀类有机功能性染料,由于具有化学、热和光稳定性较好,吸收光谱范围较宽以及荧光量⼦产率较⾼的特点,除了在传统的染(颜)料⾏业中继续发挥作⽤外,还被⼴泛应⽤于有机光导材料、有机电致发光材料、液晶显⽰材料、激光染料、化学发光⾊素、染料敏化太阳能电池和分⼦开关等领域。
新型苝酰亚胺衍生物的合成及其光学性能
结构经 Ｍ Ｈ Ｎ Ｒ和 Ｍ Ｓ表征 。用 ｕ －ｉ和荧光光谱研究 了他们 的光学性质 。 ＶＶｓ 关 键 词 ： 四酸二酐 ； 茈 菲酰亚胺 ； 合成 ； 光学性质
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Ｊ ． ｚ ４ Ａ Ｈ） ７ ２ （ ， ＝８４Ｈ ， Ｈ， ｒ ，． １ ｄ Ｊ＝８４ ｚ ８ ．Ｈ ， Ｈ， ＡＨ） ６ ８ （ ， ８４Ｈ ， Ｈ， ｒ ， ．０ ｓ ｒ ， ．７ ｄ Ｊ＝ ． ｚ ８ ＡＨ） ３５ （ ， ２ Ｈ，Ｏ ，１ ２ ｓ ６ Ｈ） ． ６（ ，３ Ｈ，Ｃ ） Ｈ３ ；ＭＳ（ Ｌ Ｉ ＭＡ Ｄ —
（ ｅｅｒｈＩｓｔｔ ｏ ｈ ｍｃｌ ｅ ｎｅ Ｂ ｉｎ ０ ２ ５ Ｃ ｉａ Ｒ ｓａｃ ｔｕ ｆ ｅ ｉ ｆ ｓ ， ｅ ｉｇ１２ ０ ， ｈｎ ） ｎｉ ｅ Ｃ ａＤ ｅ ｊ
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酸碱控制的卟啉_苝酰亚胺分子阵列荧光开关
Vol.25高等学校化学学报 No.11 2004年11月 CHEM ICAL JOU RNAL OF C HINESE UNIVERSITIES 2148～2152 酸碱控制的卟啉-酰亚胺分子阵列荧光开关孙景志1,杨新国1,2,李寒莹1,黄 骥1,汪 茫1(1.浙江大学高分子科学与工程系,浙江大学硅材料国家重点实验室,杭州310027;2.湖南大学材料科学与工程学院,长沙410082)摘要 研究了氯仿溶液中分子阵列N,N-二[对-5′-(间-10′,15′,20′-三苯基卟啉)基-苯基]-3,4∶9,10-四羧基二酰亚胺(T rP P-PT CDI-T r PP)在不同浓度的三氟乙酸作用下荧光光谱的变化,质子化无金属卟啉的光致激发态成为各种激发态中相对稳定的物种,因此无论激发无金属卟啉基元( =439nm)还是酰亚胺基元( =491nm),分子阵列都表现出质子化无金属卟啉生色团的特征荧光发射,酸的引入使激发态下高效率的电荷转移衰变途径被关闭,辐射衰变途径被打开.在溶液中引入三乙胺去质子化使电荷转移衰变途径被打开而辐射衰变途径被关闭,因此分子阵列构成了一个通过酸碱控制的荧光开关.考虑到酸碱中和反应的方便性及分子阵列对不同波段光激发同时敏感的广谱性,该分子阵列开关具有特殊优势.关键词 分子阵列;质子化;酸碱中和;荧光开关中图分类号 O631 文献标识码 A 文章编号 0251-0790(2004)11-2148-05近来的研究结果表明,卟啉-酰亚胺分子阵列在分子导线、逻辑门、分子开关等分子光电器件领域具有较好的应用前景[1～4].受光激发时,分子阵列中亚结构单元间发生瞬态电荷或能量转移,这些过程可通过在卟啉中心引入不同金属离子或者改变卟啉与酰亚胺两亚结构单元间的距离和相对取向而调节和控制[5～9].我们在最近的研究中发现,在一定浓度的CF3COOH中,无论激发卟啉基元还是酰亚胺基元,无金属卟啉-酰亚胺分子阵列都表现出质子化无金属卟啉生色团的特征荧光发射,未质子化前占主导的从卟啉到酰亚胺基元的光致电子转移衰变途径在质子化后被有效抑制,这实际上构成了以酸浓度作为调节手段,以卟啉为功能载体的荧光开关的工作原理.考虑到酸碱中和是一个可逆过程,而且远比金属配位更灵活和简便,因此我们系统地研究了无金属卟啉-酰亚胺分子阵列在CF3COOH和三乙胺调节下的荧光发射特征.1 实验部分1.1 试剂与仪器间甲酚、咪唑、无水乙醇、无水甲醇、氯仿和KOH均为分析纯试剂,3,4,9,10-四甲酸酐从Aldrich公司购买并直接使用,5-(4-氨基苯基)-10,15,20-三苯基卟啉由实验室制备,分析纯的三氟乙酸和三乙胺经减压蒸馏后使用.标准样品硫酸奎宁与罗丹明B为色谱纯试剂,参比样品四苯基卟啉与N,N-正丁-3,4∶9,10-四羧基二酰亚胺从Fluka公司购买,升华后使用.Perkin-Elm er Lambda20紫外-可见光谱仪,Shim adzu RF-540型荧光光谱仪.1.2 实验过程分子阵列N,N-二[对-5′-(间-10′,15′,20′-三苯基卟啉)基-苯基]-3,4∶9,10-四羧基二酰亚胺(T rPP-PT CDI-T rPP)的合成路线如图1所示.在装有回流冷凝管、温度计和磁力搅拌器的50mL三口瓶中加入25m L间甲酚和10m L咪唑作溶剂,在氮气保护下先加入6.3g5-(4-氨基苯基)-10,15,20-三苯基卟啉,加热溶解后,再加入1.0g收稿日期:2003-11-18.基金项目:国家自然科学基金(批准号:90101008)和吉林大学超分子结构与材料开放实验室资助.联系人简介:汪 茫(1938年出生),男,教授,主要从事有机半导体复合光电功能材料的研究.E-mail:mw ang@Fig .1 Synthetic route to molecular array of N ,N -bis [para -5′-(meso -10′,15′,20′-triphenylporphyrin )phenyl ]-peryl ene -3,4∶9,10-tetracarboxyl -diimide (TrPP -PTCDI -TrPP )的3,4,9,10-四甲酸酐,在搅拌下轻微回流10h,得到深棕色溶液.在氮气保护下降温,产物用100mL 无水甲醇沉淀,过滤并收集深紫色的固体,再用60℃的1%KOH 水溶液反复洗涤紫色固体,直到洗涤液中没有绿色荧光为止.先后以无水乙醇和氯仿洗涤得到的固体,真空干燥得产物1.04g ,产率约22.6%.FT IR(KBr), ~/cm -1:3453,1705,1670(—C O,im ides),1594,1577,1506,1472,1439,1403,1348,1253,1222,1177,966,850,827,810,801,747.元素分析C 112H 66N 10O 4计算值(%):C 83.25,H 4.12,N 8.61;实测值(%):C 84.11,H 5.03,N 9.21.将最终产物、参比样品和标准样品分别溶解于新蒸的经除水除氧处理的氯仿中,配制成10-6～10-7mol/L 的稀溶液,分别测试吸收光谱.取接近的吸收强度,并在相同激发波长下测定荧光光谱,按文献[10]提供的方法计算最终产物和参比样品的荧光量子产率.2 结果与讨论2.1 TrPP -PTCDI -TrPP 分子阵列的荧光光谱无金属卟啉(以下简称卟啉)生色团的Soret 带和酰亚胺生色团的Q 带吸收分别在418和491nm ,用这两个单色光激发,得到氯仿溶液中T rPP -PTCDI -TrPP 分子阵列的荧光光谱(见图2).当激发波长 ex =418nm 时,卟啉生色团的吸收比酰亚胺生色团大100倍以上,荧光光谱的性状以卟啉生色团为主,伴随微弱的酰亚胺生色团的荧光.与四苯基卟啉相比,分子阵列中卟啉生色团的荧光量子产率降低了86倍.说明分子阵列中的卟啉激发态主要通过电子转移到酰亚胺生色团上,形成无荧光的电荷分离激发态T rPP +-PTCDI --TrPP 或TrPP +-PTCDI 2--TrPP +物种[7],致使荧光量子产率大大降低.当 ex =491nm 时,由于分子阵列的吸收主要来自酰亚胺生色团,因此荧光光谱上主要表现出酰亚胺生色团的荧光(533和574nm 附近),同时伴随极少量的卟啉生色团的荧光(649和704nm ).但是,与N ,N -正丁-3,4∶9,10-四羧基二酰亚胺相比,酰亚胺生色团的荧光量子产率减小了2979倍,这是因为分子阵列中的酰亚胺生色团的激发态衰变的途径主要是电荷转移机制,即激发态的TrPP-PTCDI *-T rPP 通过空穴转移弛豫到TrPP +-PTCDI --TrPP 或TrPP +-PT CDI 2--T rPP +物种[7].Fig .2 Room temperature fl uorescence spectra f or TrPP -PTC DI -TrPP array in CHCl 3solution upon excitation at 418nm (A )and 491nm (B )2149N o.11孙景志等:酸碱控制的卟啉-酰亚胺分子阵列荧光开关 2.2 C F 3COOH 对TrPP -PTCDI -TrPP 吸收光谱的影响当[CF 3COOH ]从0增加到3.26×10-3mol /L 时,分子阵列的紫外-可见吸收光谱的变化见图3. Fig .3 Absorption spectra of 1.35×10-7mol /L TrPP -PTC DI -TrPP array in dif ferent CF 3COOH /C HCl 3solutions 可见,在0≤[CF 3COOH]≤3.26×10-3mol/L 的范围内,分子阵列中酰亚胺生色团的吸收特征无变化,其Q 带峰位在491和528nm 处.卟啉生色团的吸收光谱随[CF 3COOH ]变化有以下特点:当[CF 3COOH ]<3.26×10-5mol /L 时,光谱性状基本不变.当[CF 3COOH ]≥3.26×10-3mol/L 时,418nm 处卟啉的Soret 吸收带消失,演变为439nm 处的质子化卟啉的特征吸收峰[1,2],602和654nm 附近的吸收峰是质子化卟啉Q x 带的特征吸收.随着[CF 3COOH]继续增大,418nm 处的吸收减弱而439nm 处的吸收增强,同时Q x (0,0)和Q x (1,0)继续增强而Q y (1,0)和Q y (0,0)带继续减弱.当[CF 3COOH ]≥3.26×10-4m ol /L 时,B 带418nm 处吸收峰消失,只余439nm 处吸收峰;Q y (1,0)和Q y (0,0)带全部消失,Q x (0,0)带显著增强,Q x (1,0)峰从590nm 红移到600nm 附近.当[CF 3COOH ]=3.26×10-3mol /L 时,卟啉生色团的质子化达到饱和,吸收光谱的性状不再变化.2.3 CF 3COOH 对TrPP -PTC DI -TrPP 荧光光谱的影响向[T rPP-PTCDI-TrPP ]= 1.35×10-7m ol/L 的CHCl 3溶液中加入与图3相对应浓度的CF 3COOH,并在439和491nm 波长下测试荧光光谱[见图4(A)和(B)].无论激发卟啉还是酰亚胺生色团,当[CF 3COOH]≤3.26×10-6mol/L 时,光谱性状几乎不变.随着[CF 3COOH ]的增加,酰亚胺生色团的荧光强度保持不变,卟啉生色团的荧光强度急剧增加,并伴随着卟啉的特征发射峰从650nm 附近红移到670nm 附近,这两个峰分别对应着卟啉和质子化卟啉的特征发射.当[CF 3COOH ]=3.26×10-3mol /L 时,荧光达到饱和.计算发现:当[CF 3COOH ]= 3.26×10-3mol/L, ex =439nm 时,卟啉生色团的荧光量子产率增加82倍;而酰亚胺生色团的荧光量子产率基本不变;当 ex =491nm 时,卟啉生色团的荧光量子产率比没有酸存在时增加了81倍,而酰亚胺生色团的荧光量子产率降低了1817倍.显然,CF 3COOH 的加入改变了分子阵列的激发态衰变机理.Fig .4 Variations of the f luorescent spectral features for TrPP -PTCDI -TrPP array with dif ferentconcentrations of CF 3COOH upon excitation at 439nm (A )and 491nm (B )质子化使卟啉生色团带上正电荷,如果其光致激发态通过电子从卟啉转移到酰亚胺生色团形成荷电激发态,则需使卟啉负载额外的电荷,造成激发态[H 2+2T rPP +-MDPTCDI --H 2+2T rPP]比激发态[H 2+2TrPP *-MDPTCDI -H 2+2T rPP]能量更高,因此质子化卟啉生色团直接通过辐射衰变和内转换途径弛豫到基态.此外,吸收光谱特征跃迁的红移也证明质子化使HOM O 与LUM O 之间的能量差减小,2150 高等学校化学学报V ol.25即质子化卟啉的激发态比未质子化的卟啉的激发态处于能量更低的位置.质子化卟啉的本征激发态是各种激发态中相对稳定的物种,因此未质子化前占主导的从卟啉到酰亚胺基元的光致电子转移衰变途径在质子化后被有效抑制.当 ex =439nm 时,质子化卟啉生色团被激发,得到的激发态以辐射衰变方式回到基态,从而表现出比未质子化前明显增强的荧光.当 ex =491nm 时,酰亚胺生色团被激发,得到的激发态通过电荷分离态迅速弛豫到质子化卟啉的激发态,即发生[H 2+2TrPP -M DPTCDI *-H 2+2TrPP ] [H 2+2TrPP +-MDPTCDI --H 2+2TrPP ] [H 2+2TrPP *-M DPT CDI -H 2+2TrPP ]的过程,最后以辐射衰变方式弛豫到基态,辐射出质子化卟啉生色团的特征荧光.2.4 酸碱调控的荧光分子开关根据以上讨论,在中性氯仿溶液或者氯仿溶液中三氟乙酸浓度低于某阈值时,无论激发卟啉还是酰亚胺生色团,分子阵列都表现出强烈的荧光猝灭,因为激发态[TrPP *-PTCDI-TrPP]和[TrPP-PT CDI *-T rPP]都存在着高效率的超快电荷转移,形成的电荷分离态[TrPP +-PT CDI --T rPP]和[T rPP +-PTCDI 2--TrPP +]以非辐射跃迁的方式衰变.当氯仿溶液中三氟乙酸浓度高于该阈值时,由于无金属卟啉生色团被质子化,而形成的质子化卟啉生色团的光致激发态处于相对稳定的状态,因此无论激发卟啉还是酰亚胺生色团,分子阵列都表现出质子化卟啉生色团的荧光发射.如果把有荧光辐射的状态定义为“开”,则荧光猝灭的状态为“关”.图4所给出的实验事实证明,一定浓度的三氟乙酸的加入使分子阵列中卟啉生色团的荧光从关到开.可以预期,如果在质子化的分子阵列的氯仿溶液中引入适当的碱,那么质子化的卟啉生色团将因酸碱中和而恢复到卟啉状态,随之而产生的现象是荧光猝灭.图5所示的实验结果充分证实了这一点.当加入三乙胺将酸中和,使分子阵列处于中性或微碱性环境时,卟啉生色团的特征荧光显著猝灭,分子阵列高效率的电子转移过程得以恢复,分子阵列又处于“关”的状态.于是,该分子阵列构成了一个酸碱调控的荧光开关.Fig .5 Representative acid -base control led fluorescent switch based on moleculararray (3.3×10-7mol /L )in CHC l 3solutionT he fluorescence of protonated free-base porphyrin subunit is sw itched off/on before/after addition of 3.26×10-3mol/LCF 3COOH and off again by neutralization w ith triethylam ine,all upon excitation at 439nm(A)and 491nm(B).这种通过酸和碱来调控的荧光开关具有特殊的优越性.从微观机理看,荧光的“关”与“开”以激发态的电荷转移是否发生为依据,从而区别于仅仅因酸碱中和反应导致的吸收波长变化(溶致变色)作为控制机制的光开关,提供了另一类开关机制.从化学原理看,酸碱中和是最容易调节和控制的反应之一,操作远比通过复杂的化学反应使卟啉生色团的金属化方便,尽管选择适当的金属阳离子使无金属卟啉基元形成金属卟啉也可以实现电荷转移的调控[5～7].从光谱响应范围看,无金属卟啉-酰亚胺分子阵列具有较宽波段的响应.如果仅仅是开关行为,无金属卟啉已经可以完成该功能,但是仅仅靠无金属卟啉不能完成对电荷转移的控制;更重要的是,光激发酰亚胺生色团时,对此波段几乎无吸收的卟啉生色团也能发射出其特征荧光,对于某些不能使用适合卟啉基元的激发光却需要观察卟啉基元的光物理过程的特殊应用场合,卟啉-酰亚胺分子2151N o.11孙景志等:酸碱控制的卟啉-酰亚胺分子阵列荧光开关 阵列显示出单一荧光染料分子无可比拟的优势,在生物荧光标记和分子动力学研究中有独特的用途.参 考 文 献[1] O ′neil M .P .,Niemczyk M .P .,Svec W .A .et al ..Science [J ],1992,257:63—65[2] Debreczeny M.P.,Svec W.A.,Wasielew ski M.R..S cience[J],1996,274:584—586[3] Gosztol a D.,Niemczyk M.P.,Wasielew ski M.R..J.Am.Chem.Soc.[J ],1998,120:5118—5126[4] Boom T.,Hayes R.T.,Zh ao Y.et al ..J.Am.Chem.Soc.[J],2002,124:9582—9590[5] Prathapan S.,Yang S.I.,Seth J.et al ..J.Phys.Chem.B[J],2001,105:8237—8248[6] Yang S .I .,Prathapan S .,M iller M .A .et al ..J .Ph ys .Chem .B [J ],2001,105:8249—8262[7] Loew e R.S.,T omizaki K.,Youngblood W.J.et al ..J.M ater.Chem.[J],2002,12:3438—3446[8] M uthukumaran K.,Loew e S.,Kirmaier C.et al ..J.Ph ys.Chem.B[J],2003,107:3431—3442[9] Ki rm aier C.,Hindin E.,Schw artz K.et al ..J.Phys.Ch em.B[J ],2003,107:3443—3454[10] Berlman I.B..Hanbook of Fluorescence S pectra of Arom atic M olecules,2nd edn.[M ],New York :Academic Press,1971An Acid -base Controll ed Fluorescence S witch Based on a Free -base -porphyrin -perylene -diimide Mol ecular ArraySUN Jing-Zhi 1,YANG Xin-Guo 1,2,LI Han-Ying 1,HUANG Ji 1,WANG Mang1*(1.State K ey L ab of Silicon M aterials ,D ep ar tment of Poly mer Science &Engineer ing ,Zhej iang Univer sity ,H angz hou 310027,China ;2.T he College of M ater ials Science and Eng ineer ing ,H unan U niversity ,Changsha 410082,China )Abstract T he variations of the fluorescent spectral features w ith respect to a molecular array ,N ,N -bis[p -5′-(m -10′,15′,20′-triphenylporphy rin )phenyl]-perylene-3,4∶9,10-tetracarboxyl-diim ide (TrPP-PT CDI-T rPP),were investigated at different concentrations of trifluoroacetic acid,the m olecular array displays the characteristic emission of the protonated free -base -porphyrin subunit upon the photo -ex citationof both the protonated free -base -porphyrin (=439nm )and perylene -diimide subunits ( =491nm ),be-cause the ex cited state of protonated free-base-porphyrin in the molecular array w as a relative stable species in comparison w ith other ex citations.The incorporation of the acid leads to the closure of the efficient charg e transfer decay ,w hile results in the open of the radiation decay .Addition of triethylamine into the solution affords the reverse processes,i .e .the open of the efficient charg e transfer decay while the closure of the radiation decay.Thus the molecular array provides a proton-ty pe of fluorescent sw itch based on acid-base control.Such a molecular array sw itch has advantag es of facility due to the acid-base neutraliza-tion and broad -band sensitivity due to the sim ultaneous response to different excitation w avelengths .Keywords M olecular array;Protonation;Acid-base neutralization;Fluorescent sw itch(Ed.:Y,Z)2152 高等学校化学学报V ol.25。
苝的荧光性质研究新进展
创新实践论文苝的荧光性质研究进展Progresses in fluorescence properties of perylene学院：化学化工学院专业：应用化学班级：2011级3班学号：********姓名：***指导教师：***2014 年 6 月18 日创新实践课程评分表一、综述类二、研究类苝的荧光性质研究进展摘要苝及苝系衍生物具有优异的光、热和化学稳定性，对从可见区到红外区的光有很强的吸收，是一类性能特异的分子电子学材料，在激光材料、荧光探针分子、液晶显示材料、电致发光器件、场效应晶体管及太阳能电池等方面有着广泛的应用，对它们的发光性质及其他光物理性质的研究一直以来都是异常活跃的课题。
关键词；苝；荧光；荧光量子产率；晶核;Progresses in fluorescence properties of peryleneABSTRACTAs an important class of functional materials, perylene bisimide derivative possess many advantages of stable structure, oustanding photoelectron properties, high thermal stability and exhibit wide absorption and emission bands in the visible, which can be widely used in laser material, fluorescence probe, liquid crystal material, organic solid state photovoltaic device, organic thin-film field-effect transistor, organic solar cell and so on.Key words；Perylene;Fluorescence；Quantum yield; Crystal nuclei;第一部分有关苝的简介1.1苝的介绍苝是一种由五个苯环组成的芳香分子（其结构如图 1-1 所示），具有大的π-π共轭结构，是使用最早的芳香类荧光染料之一。
苝的荧光性质研究新进展
创新实践论文苝的荧光性质研究进展Progresses in fluorescence properties of perylene学院：化学化工学院专业：应用化学班级：2011级3班学号：********姓名：***指导教师：***2014 年 6 月18 日创新实践课程评分表一、综述类二、研究类苝的荧光性质研究进展摘要苝及苝系衍生物具有优异的光、热和化学稳定性，对从可见区到红外区的光有很强的吸收，是一类性能特异的分子电子学材料，在激光材料、荧光探针分子、液晶显示材料、电致发光器件、场效应晶体管及太阳能电池等方面有着广泛的应用，对它们的发光性质及其他光物理性质的研究一直以来都是异常活跃的课题。
关键词；苝；荧光；荧光量子产率；晶核;Progresses in fluorescence properties of peryleneABSTRACTAs an important class of functional materials, perylene bisimide derivative possess many advantages of stable structure, oustanding photoelectron properties, high thermal stability and exhibit wide absorption and emission bands in the visible, which can be widely used in laser material, fluorescence probe, liquid crystal material, organic solid state photovoltaic device, organic thin-film field-effect transistor, organic solar cell and so on.Key words；Perylene;Fluorescence；Quantum yield; Crystal nuclei;第一部分有关苝的简介1.1苝的介绍苝是一种由五个苯环组成的芳香分子（其结构如图 1-1 所示），具有大的π-π共轭结构，是使用最早的芳香类荧光染料之一。
含蜜胺基团的新型苝酰亚胺染料的合成及纳米纤维的构筑
基金项 目： 国家 自然科学基金（ 批 准号 ： ５ ０ ５ ７ ３ ０ １ ９ ， ５ １ ２ ７ ３ ０ ６ １ ） 、 教育 部新世纪优 秀人才支持计 划 （ 批准 号 ： Ｎ Ｃ Ｅ Ｔ 一 １ ０ ０ － ３ ７ ２ ） 和浙江 大学硅材料国家重 点实验室开放课题 （ 批准号 ： Ｓ Ｋ Ｌ ２ ０ ０ ９ － ５ ） 资助． 联系人 简介 ： 杨新 国， 男， 博士 ， 副教授 ， 主要从事超分子功能材料的组装及结构与性能研 究． Ｅ － ｍ ａ ｉ ｌ ： ｘ ｇ ｙ ｇ ＠ｈ ｎ ｕ ． ｅ ｄ ｕ ． ｃ ｎ
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高 等 学Байду номын сангаас校 化 学 学 报
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Ｓ ｈ ｉ ｍ ａ ｄ ｚ ｕ Ｕ Ｖ － ２ ５ ５ ０紫外一 可见光谱仪（ 日 本Ｓ ｈ ｉ ｍ ａ ｄ ｚ ｕ 公司） ； Ｈ ｉ ｔ ａ ｃ ｈ ｉ Ｆ － ４ ５ ０ ０ 荧光光谱仪（ 日 本Ｈ ｉ ｔ ａ ｃ ｈ ｉ 公 司） ； Ｊ Ｓ Ｍ－ ６ ７ ０ ０ Ｆ型场 发射 扫描 电子显微 镜 （ 日本 Ｊ ｅ ｏ ｌ 公 司） ； Ｏ Ｌ Ｙ Ｍ Ｐ Ｕ Ｓ Ｂ Ｘ ５ １ 偏 光 光学显 微镜 （日本 ） ； Ｅ ｌ ｅ ｍ ｅ ｎ ｔ ａ ｒ ｖ ａ ｉ ｆ ｏ １ Ｉ 元素分析仪 （ 德国 Ｅ ｌ ｅ ｍ ｅ ｎ ｔ ａ ｒ 公司） ； Ｓ ＷＧ － Ｘ ４ 显微熔点测定仪（ 上海） ． １ ． ２ ２ 。 ４ － 二（ 月桂氨 基 ） － （ １ ． 氨 基 己二氨基 ） － １ ， ３ ， ５ － 三嗪（ ２ ） 的合成
新6,有机半导体的异质结问题
费米能级
金属电极(M)
有机半导体(O)
金属电极(M) 有机半导体(O)
（a）未考虑有偶极存在的情况 左图 (a)为偶极势垒 Δ＝0 时的金属与有机 半导体间的能级关系图。 在有机材料的一侧可 以看到：有机材料的最 高占有能级（HOMO） 与最低未占有能级 （LUMO）， 以及HOMO与真空 能级间的离子化电位 IE， 和真空能级与LUMO之 间的电子亲合能（EA） 等。
不同材料界面的能级概念
在讨论有关有机半导体材料的一些基本性质与行为时， 已对其中一些能级关系、包括如HOMO ,LUMO 以及离 子化电位与电子亲和能等做了介绍。
可以在此基础上，对不同材料及其界面的能级概念， 作进一步的讨论。下面列出的是金属电极与有机材料 间界面的能级关系图。
材料的能级概念与三种不同的能级关系
在金属电极的一侧，情况比较简单。列出的仅金属的费米 能级EF 。以及相当于有机材料离子化电位的 金属功函数фM。
具有相同真空能级的异质结构
由于在左图中列出的为：无偶极存在的体系。 因此可清楚地看到：电子从金属电极注入到有机体时 的势垒为фBe 。而电子从有机层的HOMO能级注入到金 属电极时的势垒则为фBh 。 由于电子是从有机层的HOMO能级注入金属，因此也 可写作EF, HOMO（即将HOMO看作相当于有机材料的费 米能级）。 在上图的右图中，请注意：是具有不同真空能级的异 质结构。
酞菁铜与十六氟酞菁铜相互结合时的能级关系
真空能级 真空能级
5.16
偶极生成而 引起的偏移
3.12
1.7 CuPc 1.5 F16CuPc
基态下的电荷 转移方向