Cation-Induced Dimerization of Heteroleptic Crown-Substituted Trisphthalocyaninates as Revealed by X-ray Diffraction and NMR Spectroscopy
Alexander G. Martynov, Marina A. Polovkova, Georgy Berezhnoy, Anna А. Sinelshchikova, F.M. Dolgushin, Kirill P. Birin, Gayane A. Kirakosyan, Yulia G. Gorbunova, А. Yu. Tsivadze
Abstract
We report comprehensive X-ray diffraction and NMR studies of potassium-induced dimerization of heteroleptic triple-decker crown-phthalocyaninates [(15C5)4Pc]M(Pc)M(Pc) (1M, M = Y and Tb). Characterization of the crystalline dimer 2(1Y)·4KBPh4·12CH3CN·10CHCl3 gave the first structural evidence of the formation of a six-decker structure with four rare earth metal ions perfectly aligned near the symmetry axis. NMR studies of soluble supramolecular dimers 2(1M)·4KOAc provided a spectral–structural model that allowed us to assign the NMR spectra of related complexes with paramagnetic lanthanides and to further evaluate their structure and long-range interaction between the Ln(III) centers in multinuclear tetrapyrrolic complexes. The obtained results are promising for elaboration of new supramolecular magnetic materials.