Control of Conformation and Chirality of Nonplanar π-Conjugated Diporphyrins using Substituents and Axial Ligands
Control of Conformation and Chirality of Nonplanar π-Conjugated Diporphyrins using Substituents and Axial Ligands
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使用取代基和轴向配体控制非平面 π-共轭二卟啉的构象和手性
DOI：
10.1002/asia.201600105
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
S. Ito
中科院分区：
文献类型：
--
作者：
小野有人;S. Ito
吡嗪稠合锌卟啉的非平面构象可以通过选择中位芳基取代基和中心金属上的轴向配体来控制。ZnII双卟啉带有空间要求高的meso-芳基和邻位取代基，导致扭曲的手性D2构象，而在没有邻位取代基的芳基的情况下，非手性C2 h形式是优选的。通过与光学活性的1-苯乙胺配位，控制Zn Ⅱ双卟啉分子的旋向，实现了Zn Ⅱ双卟啉螺旋构象的诱导.
Nonplanar conformations of pyrazine‐fused ZnIIdiporphyrins could be controlled by the choice of themeso‐aryl substituents and an axial ligand on the central metals. ZnIIdiporphyrins bearing sterically demandingmeso‐aryl groups withortho‐substituents led to a twisted chiralD2conformation, while an achiralC2hform was preferred in the case of aryl groups withoutortho‐substituents. Helical chirality induction on ZnIIdiporphyrins in the twisted conformation was achieved by controlling their handedness of the molecular twist through coordination of optically active 1‐phenethylamine.