Li Li, Hu Chuanjiang, Shi Bo, Wang Yong
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P.R. China.
Jiangsu Key Laboratory of Technology for Polyamine, Polyol and Derived Polymers, Jiangsu Feixiang Group of Companies, Suzhou, P.R. China.
Dalton Trans. 2016 May 10;45(19):8073-80. doi: 10.1039/c6dt00570e.
A new host-guest system is formed between a benzene tricarboxamide linked zinc trisporphyrinate and a chiral monoalcohol (1-phenylethylalcohol). CD spectra show the chirality induction and inversion processes, which are controlled by the corresponding 1 : 1 and 1 : 2 coordination complexes. The binding constants calculated by UV-vis and CD spectral data are much larger than that for [Zn(TPP)] (TPP = tetraphenylporphyrin). The crystallographic structure of the host-guest complex reveals that multiple intramolecular hydrogen bonds and π-π interactions could contribute to its high binding affinity to 1-phenylethylalcohol. The DFT calculations suggest that the spatial orientations of porphyrin moieties change from the 1 : 1 complex to the 1 : 2 complex. The chirality induction and inversion processes are rationalized by the summation of pairwise interactions among multichromophores according to pairwise additivity.
一种由苯三甲酰胺连接的三锌卟啉与手性一元醇（1-苯乙醇）形成了一种新的主客体体系。圆二色光谱显示了手性诱导和反转过程，这些过程由相应的1:1和1:2配位络合物控制。通过紫外可见光谱和圆二色光谱数据计算得到的结合常数远大于[Zn(TPP)]（TPP = 四苯基卟啉）的结合常数。主客体络合物的晶体结构表明，多个分子内氢键和π-π相互作用有助于其对1-苯乙醇具有高结合亲和力。密度泛函理论计算表明，卟啉部分的空间取向从1:1络合物变为1:2络合物。根据成对加和性，通过多发色团之间的成对相互作用总和，对手性诱导和反转过程进行了合理化解释。
