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Deprotonation‐Induced Aromaticity Enhancement and New Conjugated Networks in meso ‐Hexakis(pentafluorophenyl)[26]hexaphyrin
Author(s) -
Cha WonYoung,
Lim Jong Min,
Yoon MinChul,
Sung Young Mo,
Lee Byung Sun,
Katsumata Sho,
Suzuki Masaaki,
Mori Hirotaka,
Ikawa Yoshiya,
Furuta Hiroyuki,
Osuka Atsuhiro,
Kim Dongho
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200991
Subject(s) - aromaticity , deprotonation , antiaromaticity , chemistry , conjugated system , porphyrin , singlet state , excited state , photochemistry , molecule , organic chemistry , polymer , atomic physics , ion , physics
meso ‐Hexakis(pentafluorophenyl)‐substituted neutral hexaphyrin with a 26π‐electronic circuit can be regarded as a real homolog of porphyrin with an 18π‐electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso ‐hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner NH groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono‐ and dianions of [26]hexaphyrin display sharp B‐like bands, remarkably strong fluorescence, and long‐lived singlet and triplet excited‐states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π‐electronic circuit and cause enhanced aromaticity.