Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex

被引：17

作者：

Kolomeychuk, Filipp M. ^{[1
,2
]}

Safonova, Evgeniya A. ^{[2
]}

Polovkova, Marina A. ^{[2
]}

Sinelshchikova, Anna A. ^{[2
]}

Martynov, Alexander G. ^{[2
]}

Shokurov, Alexander, V ^{[2
]}

Kirakosyan, Gayane A. ^{[1
,2
]}

Efimov, Nikolay N. ^{[1
]}

Tsivadze, Aslan Yu ^{[1
,2
]}

Gorbunova, Yulia G. ^{[1
,2
]}

机构：

[1] Russian Acad Sci, Kurnakov Inst Gen & Inorgan Chem, Moscow 119991, Russia

[2] Russian Acad Sci, Frumkin Inst Phys Chem & Electrochem, Moscow 119071, Russia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2021年 / 143卷 / 35期

基金：

俄罗斯科学基金会; 俄罗斯基础研究基金会;

关键词：

RAY CRYSTAL-STRUCTURE; SUBSTITUTED PHTHALOCYANINE; MAIN ABSORPTION; PORPHYRINS; BAND;

D O I：

10.1021/jacs.1c05831

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reversible nucleophilic addition to a phthalocyanine core was observed for the first time for the electron-deficient cationic phosphorus(V) complex [PcP(OMe)(2)](+), whose reaction with KOH afforded a highly distorted nonaromatic adduct bearing an OH group at one of the alpha-pyrrolic carbon atoms. This adduct was characterized by single-crystal X-ray diffraction, ESI HRMS, and NMR, and UV-vis spectroscopy, together with quantum-chemical modeling. The acidic treatment of this adduct restored aromaticity and recovered the starting cationic complex. The reversible aromaticity breakage resulted in dramatic changes in the photophysical properties of the studied complex, which could pave the way to novel switchable Pc-based compounds and materials.

引用

页码：14053 / 14058

页数：6

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