Theoretical Studies on the Structure and Spectrum of Imidazole-Chloranil Charge Transfer Complex

测定了咪唑-四氯苯醌电荷转移复合物在氯仿溶液中的紫外可见吸收光谱,运用Benesi-Hildebrand方程和Job连续变换法确定了咪唑-四氯苯醌电荷转移复合物的化学计量比为1:1. 采用密度泛函理论和多体微扰理论研究了咪唑-四氯苯醌电荷转移复合物的空间构型与结合能. 理论计算结果显示,咪唑-四氯苯醌电荷转移复合物共有四种可能的空间构型,分别为两种边(咪唑)-面(四氯苯醌)式结合构型(S1、S2)和两种边(咪唑)-边(四氯苯醌)式结合构型(S3、S4). 通过比较它们的结合能,发现边(咪唑)-面(四氯苯醌)式构型比边(咪唑)-边(四氯苯醌)式构型更稳定. 运用自然布居分析、电子密度拓扑分析与自然键轨道分析研究了四个构型的咪唑与四氯苯醌结合特征. 结果表明,边(咪唑)-面(四氯苯醌)式构型为电荷转移复合物,而边(咪唑)-边(四氯苯醌)式构型为分子间氢键复合物. 对于复合物最稳定构型S1,咪唑n(N15)孤电子对轨道和四氯苯醌∏* (C1=O7)反键轨道的电荷转移相互作用对咪唑-四氯苯醌复合物的稳定性起着决定性的作用,此外O7…H20氢键也起一定的作用. 采用含时密度泛函理论计算了复合物(S1)的电子激发能. 基于理论计算结果,分析了复合物的紫外-可见吸收光谱.     

Theoretical Studies on the Structure and Spectrum of Imidazole-Chloranil Charge Transfer Complex

UV-Vis absorption spectra of the molecular complex formed by imidazole (Im) and chloranil (CA) were measured in chloroform. The stoichiometry of the imidazole-chloranil (Im-CA) complex was determined as 1:1 by applying Benesi-Hildebrand's equation and Job's continuous variation method. Density function theory (DFT) and MP2 calculations were performed to study the structures and the binding energies of the Im-CA complex. The calculations located four conformations (denoted as S1-S4) for the Im-CA complex, two edge(Im)-to-face(CA) linked and two edge(Im)-to-edge(CA) linked. It was found that the edge-to-face conformers are more stable than the edge-to-edge ones. The bonding characteristics of these conformers were investigated with natural population analysis (NPA), topological analysis of electron density, and natural bond orbital (NBO) analysis. It was revealed that the edge-to-face conformers are charge-transfer (CT) complexes whereas the edge-to-edge conformers are the hydrogen bond complexes. For the most stable conformation of the Im-CA complex (S1), the charge transfer interaction of the imidazole n(N15) lone pair orbital with the chloranil ∏*(C1=O7) orbital plays a crucial role in the Im-CA binding, and the binding is further strengthened by the O7… H20 hydrogen bond. The electronic excitation energies of the complex (S1) were calculated with time-dependent DFT (TDDFT), and the observed UV-Visible spectrum of the complex was analyzed based on the computed results.