化学
氧化还原
电致变色
镧系元素
配体(生物化学)
酞菁
超分子化学
分子内力
金属
光化学
无机化学
结晶学
离子
立体化学
晶体结构
有机化学
物理化学
电极
生物化学
受体
作者
Anna А. Sinelshchikova,Anna А. Sinelshchikova,Л. A. Лапкина,V. E. Larchenko,Pavel V. Dorovatovskii,А. Yu. Tsivadze,А. Yu. Tsivadze,Yulia G. Gorbunova,Yulia G. Gorbunova
标识
DOI:10.1021/acs.inorgchem.4c00401
摘要
The redox state of the phthalocyanine in sandwich lanthanide complexes is crucial for their applications. In this work, we demonstrate that the cation-induced supramolecular assembly of crown-substituted phthalocyanine lanthanide complexes Ln[(15C5)4Pc]2 can be used to control the redox state of the ligand simultaneously with the coordination sphere of the central metal. We achieve unprecedented redox switching of phthalocyanine ligands in a double-decker Gd(III) complex, resulting from the intramolecular inclusion of potassium cations between the decks with simultaneous twisting of the ligands (the skew angle between them decreases from 44.61 to 0.21°). Such a structural change leads to an increase in the deck-to-deck distance and drastically facilitates ligand reduction. This process was shown to be anion-dependent: only potassium salts of weak acids (KOPiv and KOAc) induce intramolecular inclusion of cations with redox switching in contrast to salts of strong acids (KBr, KOPic, KSCN, and KPF6), where such a redox process does not occur. This breakthrough opens new avenues for controlling the electrochromic properties, of phthalocyanines, along with other properties, such as electrical conductivity, optics, etc.
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