Specific Features of Cation-Induced Aggregation of Tetracrown-Substituted Aluminum(III) Phthalocyaninates

Abstract

The cation-induced dimerization of tetra-(15-crown-5)-substituted Al(III) phthalocyaninate with Na+, K+ and Rb+ salts in solution has been studied by 1H NMR. It has been demonstrated that two types of supramolecular dimers coexist in solutions, which is consistent with the existence of both the monomeric and oxygen-bridged dimeric forms of the initial Al(III) complex. With the use of mass spectrometry (MALDI-TOF and HR-ESI), it has been shown that Al(III) monophthalocyaninate [(OH)AlR4Pc] forms supramolecular dimers {[M4(XAlR4Pc)2]4+(X−)4}, whereas Al(III) μ-oxodiphthalocyaninate [(AlR4Pc)2(μ-O)] forms oxygen-bridged supramolecular dimers {[M4(XAlR4Pc)2(μ-O)]2+(X−)2}.