Han Zhen, Li Li, Shi Bo, Fang Xianshi, Wang Yong, Hu Chuanjiang
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.
Inorg Chem. 2016 Apr 18;55(8):3730-7. doi: 10.1021/acs.inorgchem.5b02295. Epub 2016 Mar 29.
We have designed and synthesized a novel zinc trisporphyrinate with a benzene tricarboxamide as the linker. In the presence of a large excess of 1-phenylethylamine, single crystals of the corresponding 1:3 host-guest complex were obtained, which provide the crystallographic structure of a host-guest complex consisting of an achiral porphyrin and a chiral monoamine. The structure reveals the 1-phenylethylamines adopt the "inside" binding mode that is stabilized by intramolecular hydrogen bonds. The NH2 of the 1-phenylethylamine is involved in both coordination and hydrogen bonding interactions. Circular dichroism (CD) and ultraviolet-visible spectra revealed that the 1:3 host-guest complex is dominant in the presence of a large excess of 1-phenylethylamine. The crystal structure shows there are two diastereomers of the 1:3 host-guest complexes. Density functional theory and TDDFT calculations suggest that one of the diastereomers is more energetically favorable, which dominates the CD signals.
我们设计并合成了一种以苯三甲酰胺为连接基的新型三卟啉锌配合物。在大量过量的1-苯乙胺存在下，获得了相应1:3主客体配合物的单晶，该单晶提供了由非手性卟啉和手性单胺组成的主客体配合物的晶体结构。该结构表明1-苯乙胺采用“内部”结合模式，该模式通过分子内氢键得以稳定。1-苯乙胺的NH2参与配位和氢键相互作用。圆二色光谱（CD）和紫外可见光谱表明，在大量过量的1-苯乙胺存在下，1:3主客体配合物占主导。晶体结构表明1:3主客体配合物存在两种非对映异构体。密度泛函理论和含时密度泛函理论计算表明，其中一种非对映异构体在能量上更有利，它主导了CD信号。
