Deprotonation-Induced Aromaticity Enhancement and New Conjugated Networks in meso-Hexakis(pentafluorophenyl)[26]hexaphyrin

被引：31

作者：

Cha, Won-Young ^{[2
,3
]}

Lim, Jong Min ^{[2
,3
]}

Yoon, Min-Chul ^{[2
,3
]}

Sung, Young Mo ^{[2
,3
]}

Lee, Byung Sun ^{[2
,3
]}

Katsumata, Sho ^{[1
]}

Suzuki, Masaaki ^{[4
]}

Mori, Hirotaka ^{[4
]}

Ikawa, Yoshiya ^{[1
]}

Furuta, Hiroyuki ^{[1
]}

Osuka, Atsuhiro ^{[4
]}

Kim, Dongho ^{[2
,3
]}

机构：

[1] Kyushu Univ, Grad Sch Engn, Dept Chem & Biochem, Nishi Ku, Fukuoka 8190395, Japan

[2] Yonsei Univ, Dept Chem, Seoul 120749, South Korea

[3] Yonsei Univ, Spect Lab Funct Elect Syst, Seoul 120749, South Korea

[4] Kyoto Univ, Grad Sch Sci, Dept Chem, Sakyo Ku, Kyoto 6068502, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 49期

基金：

新加坡国家研究基金会;

关键词：

aromaticity; deprotonation; expanded porphyrins; porphyrinoids; ultrafast spectroscopy; INDEPENDENT CHEMICAL-SHIFTS; EXPANDED PORPHYRINS; MOBIUS AROMATICITY; PHOTOPHYSICAL PROPERTIES; CONFORMATIONAL-CHANGES; 2-PHOTON ABSORPTION; FIGURE EIGHTS; STATE; HEXAPHYRINS; PROTONATION;

D O I：

10.1002/chem.201200991

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26p-electronic circuit can be regarded as a real homolog of porphyrin with an 18p-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 N?H 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 p-electronic circuit and cause enhanced aromaticity.

引用

页码：15838 / 15844

页数：7

共 73 条

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