摘要
反芳香性缩环卟啉衍生物在结构上比常规的18π共轭芳香性卟啉有着更少的吡咯单元或中位碳,同时具有4nπ共轭体系,其代表性分子包括16π共轭的去甲咔咯、咔咯和三元卟啉等.反芳香性缩环卟啉在结构上具有分子刚性强、稳定性好、易于功能化等特点,同时在性能上具有顺磁诱导环电流强、环外磁屏蔽效应强、最高电子占据轨道-最低电子未占据轨道(HOMO-LUMO)能级差小和电荷传递能力强等特性.本文介绍了反芳香性缩环卟啉近年来在合成和功能化修饰方面的研究进展,展现了其在基于芳香性-反芳香性转换的光电材料、可充电电池电极材料和超分子导电材料等领域的应用价值.
Antiaromatic ring-contracted porphyrinoids have fewer pyrrole units or meso carbons than standard 18π-conjugated aromatic porphyrins and exhibit a 4nπ-conjugation system,with representative molecules including 16π-conjugated norcorrole,corrole,and triphyrin.Antiaromatic ring-contracted porphyrins exhibit great molecular rigidity,excellent stability,and simplicity of functionalization,as well as intense paratropic induced ring current,strong magnetic shielding effect,small highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)energy gap,and high charge transfer capability.This review introduces recent advances in the synthesis and functionalization of antiaromatic ring-contracted porphyrins,and highlights their promising utility in electronic materials based on aromatic-antiaromatic conversion,rechargeable battery electrode materials,and supramolecular conductive materials.
作者
吴凡
沈珍
Fan Wu;Zhen Shen(State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2022年第8期1321-1330,共10页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(编号:22071103,22001119,21911540069)资助项目。
关键词
缩环卟啉
反芳香性
π共轭
去甲咔咯
咔咯
三元卟啉
ring-contracted porphyrinoids
antiaromaticity
π-conjugation
norcorrole
corrole
triphyrin
