含氮杂环配体及配合物的合成、结构及其量子化学理论研究
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摘要
合成了一系列苯并咪唑衍生物及其金属配合物，采用红外、~1H和~(13)C核磁共振等分析手段对这些化合物进行了表征和谱学性质研究。并且解析了七种有代表性的该类化合物的晶体结构。研究了这些化合物的结构和性质之间的关系。
研究了苯并咪唑衍生物及其金属配合物的热分解机理、荧光性质和磁性。并应用量子化学方法系统地研究了苯并咪唑衍生物的热分解过程，提出了苯并咪唑衍生物热分解的理论判据，即键级最小原理。
应用密度泛函B3LYP／6-31G的方法系统地研究了六十种苯并咪唑衍生物的几何构型、电荷分布、红外光谱和热力学函数，为苯并咪唑化学的研究提供了大量详实可靠的基础数据。
报道了苯并咪唑与氮(NH_3)、甲胺(CH_3NH_2)、二甲胺[(CH_3)_2NH]和三甲胺[(CH_3)_3N]形成的系列复合物的理论研究结果。把复合物看作一个超分子，应用密度泛函理论，在B3LYP／6-31G水平上计算了该系列复合物的电子结构与相关性质，如稳定性、电荷转移及主要几何参数的变化规律等。结果表明，形成复合物的稳定性次序为NH_3＞CH_3NH_2＞(CH_3)_2NH＞(CH_3)_3N。形成复合物的过程包含着电荷转移。该系列复合物的稳定性与电荷转移量、前沿轨道能量差Δε_(L-H)及广义氢键距离有良好的线性关系，与结合点的电荷分布也有密切的关系。复合物的稳定性是分子间氢键作用和静电作用的综合作用结果。
针对国际上对金属配合物同DNA间作用机理的争议，采用分子模拟手段在MM+力场下，搭建并优化了金属配合物Co[L]_2Cl_2 [L为配体2-(2′，4′-二氯苯氧基甲基)苯并咪唑]及DNA[(GCGCTTAAGCGC)_2]的模型，继而对其相互作用进行了模拟。得出结论是：对所选的DNA片断，该金属配合物从大沟插入明显占优势。
以INDO／SCI方法为基础，采用自编程序计算了4-[2′-苯并咪唑基]苯甲酸内盐(1)、2-硝基苯并咪唑(2)和4-[2′-苯并咪唑基]苯甲酸(3)的偶极矩和二阶非线性光学系数。计算表明分子1具有较大的二阶非线性极化率。在此基础上，研究了分子1的系列衍生物的二阶非线性光学性质。结果表明，这类化合物具有较大的μ*β_μ值，所以，它们是一类很有前途的二阶非线性光学候选材料。
合成了一系列二硫代氨基甲酸配体既其金属配合物，培养了这些配合物的单晶，并解析了其晶体结构。
A series of novel derivatives of benzimidazole and their complexes were synthesized. Their structure were characterized by IR, 1H NMR and 13C NMR spectroscopy. Seven typical crystal structure have been studied by X-ray crystallography, and the relationship between structures and properties were presented in this paper.
Thermal decomposition mechanism, fluorescence and magnetic properties of titled complexes were investigated. The procedure of thermal decomposition has been calculated by means of quantum chemistry and the theoretical criterion of their thermal decomposition, i.e. the principle of least bond order may be used here.
Sixty kinds of titled complexes have been studied by using of density function theory(DFT) at the B3LYP/6-31G level, and their full optimized molecular geometry, charges distribution, IR spectra and thermodynamic function were presented.
The theoretical studies on a series of complexes formed from amine [CH3NH2, ( CH3) 2NH and ( CH3) 3N] or ammonia(NH3) with benzimidazole were performed using DFT method at B3LYP/6-31G level. The electronic structure and its related properties, for example, relative stability, the charge transfer between the donor and accepter, and the change of geometric parameters of the complexes were investigated. The results show that the stability of the complexes is in the order of NH3>CH3NH2>(CH3)2NH> (CH3)3N. An obvious charge-transfer was observed in the process of forming the complexes. The stability of the series of complexes keeps a good linear relation to the CT amount, the energy gap L-H between LUMO and HOMO, and the distance of extended Hydrogen bond respectively . In addition, the stability is also related to the atomic net charges of the donor center and accepter center, etc. The stability of the complexes may be caused both hydrogen bond interaction and electrostatic interaction between the molecules. Th
e calculation results might be better used to explain some experimental phenomena and regularities.
Molecular simulation methods have been applied to characterization of
the interaction between the complex Co[L]2Cl2[where L=2- (2',4'-Dichloro-phenoxymethyl)-1H-benzimidazole] and DNA[ ( GCGCTTAAGCGC) 2] in MM+ force field. Their interactions have been studied. The results show that: the intercalation on major groove is dominant.
Based on the INDO/SCI method, the dipole moment u and the nonlinear second-order polarizability Bu of compounds 4-(1H-benzimidazole-3-ium-2-yl) benzoate(1), 2-ntro-1H-benzimidazole(2) and 4-(1H-Benzimidazol-2-yl) benzoic acid (3) were calculated by using of our program. The calculated results indicate that molecule 1 has higher second-order nonlinear optical polarizability. According to this studies, the second-order nonlinear optical properties of derivatives of molecule 1 were studied as well. The results show that: Those derivatives have higher values. Therefore they are good future materials of second-order nonlinear optics.
A series of dithiocarbamate metal complexes have been synthesized and their crystal structures have been determined by X-ray single-crystal structure diffraction
研究了苯并咪唑衍生物及其金属配合物的热分解机理、荧光性质和磁性。并应用量子化学方法系统地研究了苯并咪唑衍生物的热分解过程，提出了苯并咪唑衍生物热分解的理论判据，即键级最小原理。
应用密度泛函B3LYP／6-31G的方法系统地研究了六十种苯并咪唑衍生物的几何构型、电荷分布、红外光谱和热力学函数，为苯并咪唑化学的研究提供了大量详实可靠的基础数据。
报道了苯并咪唑与氮(NH_3)、甲胺(CH_3NH_2)、二甲胺[(CH_3)_2NH]和三甲胺[(CH_3)_3N]形成的系列复合物的理论研究结果。把复合物看作一个超分子，应用密度泛函理论，在B3LYP／6-31G水平上计算了该系列复合物的电子结构与相关性质，如稳定性、电荷转移及主要几何参数的变化规律等。结果表明，形成复合物的稳定性次序为NH_3＞CH_3NH_2＞(CH_3)_2NH＞(CH_3)_3N。形成复合物的过程包含着电荷转移。该系列复合物的稳定性与电荷转移量、前沿轨道能量差Δε_(L-H)及广义氢键距离有良好的线性关系，与结合点的电荷分布也有密切的关系。复合物的稳定性是分子间氢键作用和静电作用的综合作用结果。
针对国际上对金属配合物同DNA间作用机理的争议，采用分子模拟手段在MM+力场下，搭建并优化了金属配合物Co[L]_2Cl_2 [L为配体2-(2′，4′-二氯苯氧基甲基)苯并咪唑]及DNA[(GCGCTTAAGCGC)_2]的模型，继而对其相互作用进行了模拟。得出结论是：对所选的DNA片断，该金属配合物从大沟插入明显占优势。
以INDO／SCI方法为基础，采用自编程序计算了4-[2′-苯并咪唑基]苯甲酸内盐(1)、2-硝基苯并咪唑(2)和4-[2′-苯并咪唑基]苯甲酸(3)的偶极矩和二阶非线性光学系数。计算表明分子1具有较大的二阶非线性极化率。在此基础上，研究了分子1的系列衍生物的二阶非线性光学性质。结果表明，这类化合物具有较大的μ*β_μ值，所以，它们是一类很有前途的二阶非线性光学候选材料。
合成了一系列二硫代氨基甲酸配体既其金属配合物，培养了这些配合物的单晶，并解析了其晶体结构。
A series of novel derivatives of benzimidazole and their complexes were synthesized. Their structure were characterized by IR, 1H NMR and 13C NMR spectroscopy. Seven typical crystal structure have been studied by X-ray crystallography, and the relationship between structures and properties were presented in this paper.
Thermal decomposition mechanism, fluorescence and magnetic properties of titled complexes were investigated. The procedure of thermal decomposition has been calculated by means of quantum chemistry and the theoretical criterion of their thermal decomposition, i.e. the principle of least bond order may be used here.
Sixty kinds of titled complexes have been studied by using of density function theory(DFT) at the B3LYP/6-31G level, and their full optimized molecular geometry, charges distribution, IR spectra and thermodynamic function were presented.
The theoretical studies on a series of complexes formed from amine [CH3NH2, ( CH3) 2NH and ( CH3) 3N] or ammonia(NH3) with benzimidazole were performed using DFT method at B3LYP/6-31G level. The electronic structure and its related properties, for example, relative stability, the charge transfer between the donor and accepter, and the change of geometric parameters of the complexes were investigated. The results show that the stability of the complexes is in the order of NH3>CH3NH2>(CH3)2NH> (CH3)3N. An obvious charge-transfer was observed in the process of forming the complexes. The stability of the series of complexes keeps a good linear relation to the CT amount, the energy gap L-H between LUMO and HOMO, and the distance of extended Hydrogen bond respectively . In addition, the stability is also related to the atomic net charges of the donor center and accepter center, etc. The stability of the complexes may be caused both hydrogen bond interaction and electrostatic interaction between the molecules. Th
e calculation results might be better used to explain some experimental phenomena and regularities.
Molecular simulation methods have been applied to characterization of
the interaction between the complex Co[L]2Cl2[where L=2- (2',4'-Dichloro-phenoxymethyl)-1H-benzimidazole] and DNA[ ( GCGCTTAAGCGC) 2] in MM+ force field. Their interactions have been studied. The results show that: the intercalation on major groove is dominant.
Based on the INDO/SCI method, the dipole moment u and the nonlinear second-order polarizability Bu of compounds 4-(1H-benzimidazole-3-ium-2-yl) benzoate(1), 2-ntro-1H-benzimidazole(2) and 4-(1H-Benzimidazol-2-yl) benzoic acid (3) were calculated by using of our program. The calculated results indicate that molecule 1 has higher second-order nonlinear optical polarizability. According to this studies, the second-order nonlinear optical properties of derivatives of molecule 1 were studied as well. The results show that: Those derivatives have higher values. Therefore they are good future materials of second-order nonlinear optics.
A series of dithiocarbamate metal complexes have been synthesized and their crystal structures have been determined by X-ray single-crystal structure diffraction
引文
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