Redox-Dependent Transformation of a Hydrazinobuckybowl between Curved and Planar Geometries

被引：53

作者：

Higashibayashi, Shuhei ^{[1
]}

Pandit, Palash ^{[1
]}

Haruki, Rie ^{[2
]}

Adachi, Shin-ichi ^{[2
]}

Kumai, Reiji ^{[2
]}

机构：

[1] Inst Mol Sci, Okazaki, Aichi 4448787, Japan

[2] High Energy Accelerator Res Org, Inst Mat Struct Sci, Photon Factory, Tsukuba, Ibaraki 3050801, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 36期

基金：

日本学术振兴会;

关键词：

cations; conformation analysis; heterobuckybowls; heterocycles; redox chemistry; ELECTRON-TRANSFER DISPROPORTIONATION; MOLECULAR-BOWL HYDROCARBONS; HIGH-TEMPERATURE SYNTHESIS; OPEN GEODESIC POLYARENE; INTERIOR CARBON-ATOMS; INVERSION BARRIER; PHYSICAL-PROPERTIES; ENANTIOSELECTIVE SYNTHESIS; FULLERENES SYNTHESIS; STRUCTURAL-ANALYSIS;

D O I：

10.1002/anie.201605340

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A red-fluorescent heterobuckybowl with an embedded hydrazine structure was synthesized from a cyclobiphenothiazine derivative via a strained cyclobicarbazole. The hydrazinobuckybowl was found to possess bowl and twist structures in the neutral state, a shallow bowl structure in the monocation state, and a planar structure in the dication state by means of X-ray crystallographic analysis, DFT calculations, and a comparison of experimental and calculated (CNMR)-C-13 chemical shifts. The hydrazinobuckybowl is the first buckybowl that changes its geometry between curved bowl/twist structures and a planar structure depending on the oxidation state. The drastic geometrical change was possible as a result of the presence of two heteroatoms in the bowl skeleton and the multiple reversible redox reactions of the compound. Owing to the two kinds of bowl and twist conformations, the bowl-inversion dynamics of the hydrazinobuckybowl were found to follow a triple-well potential model.

引用

页码：10830 / 10834

页数：5

共 71 条

[1] A molecular bowl sumanene [J].