Cation-Induced Dimerization of Heteroleptic Crown-Substituted Trisphthalocyaninates as Revealed by X-ray Diffraction and NMR Spectroscopy

Alexander G Martynov; Marina A Polovkova; Georgy S Berezhnoy; Anna A Sinelshchikova; Fedor M Dolgushin; Kirill P Birin; Gayane A Kirakosyan; Yulia G Gorbunova; Aslan Yu Tsivadze

doi:10.1021/acs.inorgchem.0c01346

Cation-Induced Dimerization of Heteroleptic Crown-Substituted Trisphthalocyaninates as Revealed by X-ray Diffraction and NMR Spectroscopy

Inorg Chem. 2020 Jul 6;59(13):9424-9433. doi: 10.1021/acs.inorgchem.0c01346. Epub 2020 Jun 19.

Authors

Affiliations

¹ Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31-4, Moscow 119071, Russia.
² Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky pr. 31, Moscow 119991, Russia.
³ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Vavilova str. 28, Moscow 119991, Russia.

PMID: 32559093
DOI: 10.1021/acs.inorgchem.0c01346

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.