Synthesis, Fluorescence and Dielectric Properties of Two Novel Compounds Based on Triethyl

2019. 4 Vol. 38, No. 4 Chinese J. Struct. Chem. 605─612Synthesis, Fluorescence and Dielectric Propertiesof Two Novel Compounds Based onTriethylenediamine Derivatives①DENG Si-Yu QIAN XiuLI Mu CHEN Li-Zhuang②(School of Environmental and Chemical Engineering,Jiangsu University of Science and Technology, Zhenjiang 212003, China)ABSTRACT Two compounds C8H18N2Br3Mn0.5 (1) and C12H26N2Cl4Mn (2) based on triethylene- diamine derivatives were synthesized by solution method and were characterized by elemental analysis, infrared spectroscopy, single-crystal X-ray structure analysis, fluorescence test, circular dichroism (CD) analysis and dielectric measurement, respectively. According to single-crystal X-ray determination, compound 1crystallizes in the cubic system, space group Pa3with a= b= c=13.7246(5) Å, Z = 24, V = 2585.2(3) Å3; and compound 2 crystallizes in the orthorhombic system,space group P212121 with a = 7.9716(13), b = 15.309(3), c = 15.804(3) Å, Z = 4 and V = 1928.7(6) Å3. Fluorescent analysis of compound 1showed an intense emission band at 670 nm when the exciting radiation was set at 378 nm and fluorescent analysis of compound 2showed an intense emission band at 515 nm when the exciting radiation was set at 363 nm. Dielectric constants of compounds 1 and 2 were measured at different frequencies with temperature variation.Keywords: triethylenediamine derivatives, fluorescent compounds, crystal structure,permittivity properties; DOI: 10.14102/ki.0254-5861.2011-20861 INTRODUCTIONEnergy-saving fluorescent lamps have become the focus of attention in various countries due to energy shortages[1-9]. In the past decade, rare-earth-doped LED luminescence phosphors such as nitrides, oxynitrides, silicates, aluminates, tetravalent man- ganese ions, etc. have been reported[10-18]. Most of these phosphors are based on rare earth oxides, which make their prices high. In order to overcome the shortcomings in the existing technology, two simple and reasonable fluorescent compounds, a preparation method and applications of them are provided herein. Compounds C8H18N2Br3Mn0.5 (1) and C12H26N2Cl4Mn (2) are obtained by the combination of small organic molecules with transi- tion metal salts. Their raw materials for material preparation have ample sources, low production costs, high yields and good repeatability. At the same time, the thermal decomposition temperature is relatively high and the crystal particles are uniform.2 EXPERIMENTAL2. 1 Materials and physical measurementsAll chemicals (except for ligand dabco) obtainedReceived 29 May 2018; accepted 21 August 2018 (CCDC1826194 and 1826201)①This work was financially supported by the National Natural Science Foundation of China (21671084), Six Talent Peaks Project in JiangsuProvince (2014-XCL-008), the Qing Lan Project of Jiangsu Province and the Foundation of Jiangsu Educational Committee (16KJB430011) ②Corresponding author. Doctor. E-mail: clz1977@DENG S. Y. et al.: Synthesis, Fluorescence and Dielectric Properties606 of Two Novel Compounds Based on Triethylenediamine Derivatives No. 4from Shanghai Jingchun Biochemical Technology Co., Ltd. were of reagent grade and used without further purification. Infrared spectra were recorded on a Bruker Vector 22 spectrophotometer as KBr particles in the 4000～400 cm-1region. Elemental analyses were taken on a Perkin-Elmer 240C elemental analyzer. Thermo gravimetric analyses (TGA) were conducted on a NETZSCH TG 209 F3 thermo gravimeter at a heating rate of 10 K/min in a N2atmosphere. Fluorescence properties of com- pounds 1and 2were investigated using a Spectro- fluorometer FS5 fluorescence tester.2. 2 Preparation of compound 1At room temperature, 10 mmol of manganese bro- mide and 10 mmol of dibrominated 1,4-dimethyl- 1,4-diazabicyclo [2.2.2] octane were placed in a beaker at a flow rate of 10 ml/min. Slowly adding distilled water and stirring to dissolve, the volume of distilled water is respectively 10 mL, and then the two beaker solutions are fused with each other. After stirring, the mixture was allowed to stand at room temperature for 7 days to obtain compound 1 C8H18N2Br3Mn0.5 (Scheme 1). IR data (KBr pellet, ν(cm-1)): 3381(s), 1628(m), 1466(m), 1142(w), 1048(w), 845(w), 603(m) (Fig. S1). Anal. Calcd. (%) for C8H18N2Br3Mn0.5: C, 23.47; H, 4.43; N, 6.84. Found (%): C, 23.42; H, 4.49; N, 6.88.Syntheses of compounds 1 and 22. 3 Preparation of compound 2At room temperature, 10 mmol of manganese chloride and 10 mmol of dibrominated 1,4-dipropyl- 1,4-diazabicyclo [2.2.2] octane were placed in a beaker at a flow rate of 10 ml/min. Slowly adding distilled water and stirring to dissolve, the volume of distilled water is respectively 10 mL, and then the two beaker solutions are fused with each other. After uniformly stirring, the mixture was allowed to stand at room temperature for 7 days to obtain compound 2 C12H26N2Cl4Mn (Scheme 1). IR data (KBr pellet, ν(cm-1)): 3414(m), 2983(m), 1628(m), 1466(s), 1385(s), 1203(m), 1109(s), 1055(m), 954(m), 853(s), 751(m), 677(w), 549(m) (Fig. S2). Anal. Calcd. (%) for C12H26N2Cl4Mn: C, 36.48; H, 6.63; N, 7.09. Found (%): C, 36.43; H, 6.68; N, 7.02.2. 4 Single-crystal X-ray diffractionSingle crystals of 1and 2were selected with appropriate dimensions for data collection on a Rigaku SCXmini diffractometer equipped with a graphite-monochromated Mo Kαradiation (λ= 0.71073 Å) using an ω scan mode at room tem- perature. The absorption correction was carried out by a multi-scan method. The structures were solved by direct methods with SHELXS-97 and refined by full-matrix least-squares on F2 with SHELXL-97[19, 20]. All non-hydrogen atoms were refined with aniso- tropic thermal parameters. All non-hydrogen atoms2019 Vol. 38 Chinese J. Struct. Chem. 607were refined with anisotropic thermal parameters. All hydrogen atoms attached to C, N and O atoms were added theoretically and refined with a riding model and fixed isotropic thermal parameters.2. 5 Thermo gravimetric analysisThermo gravimetric analyses (TGA) were con- ducted on a NETZSCH TG 209 F3 thermogravime- ter at a heating rate of 10 K/min in a N2 atmosphere (Figs. S3–S4).2. 6 Dielectric measurementsThe compound dielectric permittivity (ε = ε'﹣iε") was measured on a Tonghui TH2828A in the frequency range from 500 Hz to 1 MHz from –60 to 40 ℃at the AC voltage of 1 V. A pellet sample was prepared at 10 MPa and the pressed powder pellet deposited with silver-conducting glue was used for the dielectric studies.3 RESULTS AND DISCUSSION3. 1 Description of compound 1At 296 K, the crystals belong to the tripartite, Pa3 space group. The cell parameters of 1measured at 296 K are as follows: a = 13.7246(5), b = 13.7246(5), c = 13.7246(5) Å, V = 2585.2(3) Å3 and Z = 24. The view of asymmetry unit of 1 at 296 K is shown in Fig. 1. The Mn atom is in a distorted octahedral environ- ment and coordinate to six bromine atoms respec- tively; the modified triethylenediamine ring is in a twisted state, and the NCCN torsion angle in triethylenediamine is 20.502(252)°. In this structure, all Mn−Br bonds are as long as 2.7530(3) Å, which are comparable to the reported values[21-23]. The bond angle of Br−Mn−Br is 89.617(8)°. The space stacking structure of compound 1can be better displayed along a certain direction. Observing along the b axis, the distance between every two Mn atoms is 9.7048(3). Detailed information about the crystal data and structure determination for the title com- pound 1is summarized in Table 1. Selected bond distances and bond angles are given in Table 2.Table 1. Crystallographic Data for 1 and 2 at 296 K T (K) 296 296Empirical formula C8H18N2Br3Mn0.5C12H26N2C l4Mn Formula weight 136.48 395.09Crystal system Cubic OrthorhombicSpace group Pa3P212121a (Å) 13.7246(5) 7.9716(13)b (Å) 13.7246(5) 15.309(3)c (Å) 13.7246(5) 15.804(3)α (o) 90 90β (o) 90 90γ (o) 90 90V (Å3) 2585.2(3) 1928.7(6)Z 24 4D c (g/m3) 2.104 1.361μ(mm-1) 9.795 1.229F(000) 1580 820θ range (º) 2.571to 27.264 2.578 to 24.998 Collected reflections 767 3376Unique reflections 692 2385R, wR (I > 2σ(I)) 0.0193, 0.0495 0.0884, 0.2333R, wR(all data) 0.0230, 0.0510 0.1122, 0.2506 GOOF 1.035 0.999DENG S. Y. et al.: Synthesis, Fluorescence and Dielectric Properties608 of Two Novel Compounds Based on Triethylenediamine Derivatives No. 4 Table 2. Selected Bond Lengths (Å) and Bond Angles (°) of 1Bond Dist. Bond Dist. Bond Dist.Mn(2)–Br(1) 2.7530(3) Mn(2)–Br(1)#7 2.7530(3) Mn(2)–Br(1)#8 2.7530(3)Mn(2)–Br(1)#9 2.7530(3) Mn(2)–Br(1)#10 2.7530(3) Mn(2)–Br(1)#112.7530(3)Angle (°) Angle (°) Angle (°)Br(1)–Mn(2)–Br(1)#889.617(8) Br(1)#8–Mn(2)–Br(1)#1189.617(8) Br(1)#10–Mn(2)–Br(1)#1189.617(8) Br(1)#7–Mn(2)–Br(1)#1089.617(8) Br(1)#7–Mn(2)–Br(1)#989.617(8) Br(1)–Mn(2)–Br(1)#989.617(8) Symmetry transformation: #7–0.5 + x, 0.5 – y, –z; #80.5 – x, 0.5 + y, z; #9–0.5 + x, y, 0.5 – z; #101 – x, –y, –z; #110.5 – x, –y, 0.5 + zFig. 1. Coordination environment of 1 at 296 K3. 2 Description of compound 2At 296 K, the crystals belong to orthorhombic, P212121 chiral space group. The cell parameters of 2 measured at 296 K are as follows: a = 7.9716(13), b = 15.309(3), c = 15.804(3) Å, V = 1928.7(6) Å3 and Z = 4. The view of asymmetry unit of compound 2 at 296 K is shown in Fig. 2. The Mn atom is in a dis- torted tetrahedral environment and coordinates to four Cl atoms, respectively. The brominated pro- pane-modified triethylenediamine is in a twisted state. The twist angle of N(1)−C(3)−C(4)−N(2) is −16.809(1920)°, N(1)−C(1)−C(2)−N(2) is −8.666(1988)° and N(1)−C(5)−C(6)−N(2) is −12.471(1769)°. In this structure, the Mn–Cl bond lengths are 2.406(4) to 2.456(3) Å and the bond angles of Cl−Mn−Cl are 106.23(14)° to 111.89(15)°, which are comparable to the reported values[24-27]. The space stacking structure of compound 2can be better displayed along a certain direction. Observing along the a axis, ligand molecules are regularly arranged in a similar V-shaped wave. Detailed infor- mation about the crystal data and structure determi- nation for the title compound 2is summaryzed in Table 1. Selected bond distances and bond angles are given in Table 3.Table 3. Selected Bond Lengths (Å) and Bond Angles (°) of 2Bond Dist. Bond Dist. Bond Dist.Mn(1)–Cl(1) 2.455(4) Mn(1)–Cl(2) 2.406(4) Mn(1)–Cl(3) 2.456(3) Mn(1)–Cl(4) 2.449(4)Angle (°) Angle (°) Angle (°)Cl(1)–Mn(1)–Cl(3) 109.52(14) Cl(2)–Mn(1)–Cl(3) 111.89(15) Cl(2)–Mn(1)–Cl(4) 110.87(15) Cl(1)–Mn(1)–Cl(4) 106.23(14)3. 3 Fluorescence propertyThe synthesized ligand has no fluorescence, but it can produce fluorescence when the ligand binds with metal ions, which may be due to ligand-metal charge transfer (LMCT) or metal-ligand charge transfer (MLCT)[28, 29]. Fluorescence properties of compound 1 were investigated using a Spectrofluorometer FS5 fluorescence tester. The fluorescence emission2019 Vol. 38 Chinese J. Struct. Chem. 609spectrum of this compound is shown in Fig. 3. It is found from Fig. 3 that the excitation wavelength is 378 nm and the emission wavelength is 670 nm. The emission range is in the red range. Fluorescence properties of compound 2 were investigated using aSpectrofluorometer FS5 fluorescence tester. Thefluorescence emission spectrum of this compound is shown in Fig. 4. It is found from Fig. 4 that the excitation wavelength is 363 nm and the emission wavelength is 515 nm. The emission range is in the green range. These suggest that both compounds 1 and 2 may be good visible luminescent materials.Fig. 2. Coordination environment of 2 at 296 KFig. 3. Fluorescence emission of 1 Fig. 4. Fluorescence emission of 23. 4 CD spectrumAccording to the P 212121 space group of com- pound 2, the study on its chirality is conducted. As shown in Fig. 5, compound 2 has appeared the correspondingly higher peaks at a wavelength of about 210 nm. This indicates that compound 2 is homochiral.3. 5 Permittivity propertiesThe experiments test the dielectric properties of compounds 1 and 2. The permittivity of powdered samples of 1 and 2 in the form of pellets was measured (Figs. S5–S6), which are similar to the reported results before [30,31]. The temperaturedependence of the dielectric constant at differentfrequency range shows that the dielectric constants (ε1) gradually increase with a rise of temperature (–60～40 ℃), as shown in Figs. 6 to 7. In addition, compounds 1 and 2 have no obvious dielectric response (ε = ε1 – i ε2, in which ε1 and ε2 are the corresponding real and imaginary parts of dielectric constant, dielectric dissipation factor D = tan δ = ε2/ε1).4 CONCLUSIONIn this work, two novel compounds have been synthesized based on triethylenediamine derivatives and structurally characterized. 1 was demonstrated toDENG S. Y . et al.: Synthesis, Fluorescence and Dielectric Properties610 of Two Novel Compounds Based on Triethylenediamine Derivatives No. 4display red fluorescence emissions and 2 was demonstrated to display green fluorescence emis-sions in the solid state at room temperature, sug-gesting these two compounds have potential appli- cations in photoactive materials.Fig. 5. Circular dichroism (CD) of compound 2 using KBr pellets at room temperatureFig. 6. Dielectric constants of compound 1 of temperature dependence from –60 to 40 ℃ at different frequency ranges in the heating processFig. 7. Dielectric constants of compound 2 of temperature dependence from –60 to 40 ℃ at different frequency ranges in the heating process2019 Vol. 38 Chinese J. Struct. Chem. 611 REFERENCES(1)Sun, X. F.; Li, P. F.; Liao, W. Q.; Wang, Z. X.; Gao, J. X.; Ye, H. Y.; Zhang, Y. Notable broad dielectric relaxation and highly efficient redphotoluminescence in a perovskite-type compound: (N-methylpyrrolidinium)MnCl3. Inorg. Chem. 2017, 56, 19123–19128.(2)Zhou, L.; Zheng, X.; Shi, P. P.; Zafar, Z.; Ye, H. Y.; Fu, D. W.; Ye, Q. Switchable nonlinear optical and tunable luminescent properties triggeredby multiple phase transitions in a perovskite-like compound. Inorg. Chem.2017, 56, 3238–3244.(3)Chen, L. Z.; Zou, J.; Gao, Y. M.; Wan, S.; Huang, M. N. 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