Kolomeychuk Filipp M, Safonova Evgeniya A, Polovkova Marina A, Sinelshchikova Anna A, Martynov Alexander G, Shokurov Alexander V, Kirakosyan Gayane A, Efimov Nikolay N, Tsivadze Aslan Yu, Gorbunova Yulia G
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991, Russia.
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, bldg. 4, Moscow 119071, Russia.
J Am Chem Soc. 2021 Sep 8;143(35):14053-14058. doi: 10.1021/jacs.1c05831. Epub 2021 Aug 23.
Reversible nucleophilic addition to a phthalocyanine core was observed for the first time for the electron-deficient cationic phosphorus(V) complex [PcP(OMe)], whose reaction with KOH afforded a highly distorted nonaromatic adduct bearing an OH group at one of the α-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.
首次观察到缺电子阳离子磷（V）配合物[PcP(OMe)]对酞菁核的可逆亲核加成反应，该配合物与KOH反应生成了一种高度扭曲的非芳香加合物，在其中一个α-吡咯碳原子上带有一个OH基团。通过单晶X射线衍射、电喷雾高分辨率质谱、核磁共振和紫外-可见光谱以及量子化学建模对该加合物进行了表征。该加合物经酸处理后恢复了芳香性并重新得到起始阳离子配合物。可逆的芳香性断裂导致所研究配合物的光物理性质发生显著变化，这可能为新型可切换酞菁基化合物和材料开辟道路。
