1H NMR spectral analysis of structural features in a series of paramagnetic homoleptic binuclear triple-decker phthalocyaninato lanthanide complexes. (1st June 2022)

• Record Type: Journal Article
• Authors: Martynov, Alexander G.; Polovkova, Marina A.; Kirakosyan, Gayane A.; Zapolotsky, Evgeny N.; Babailov, Sergey P.; Gorbunova, Yulia G.
• Is Part Of: Polyhedron. Volume 219(2022)
• Publication Date: 2022-06-01
• Subjects: NMR spectroscopy -- Lanthanides -- Phthalocyanines -- Lanthanide-induced shift -- Spin-spin relaxation -- DFT calculations; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2022.115792
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Analysis of the lanthanide-induced shifts and relaxation rates in 1 H NMR spectra of a series of tetra-15-crown-5-phthalocyanine complexes with Nd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+ and Tm 3+ showed the isostructurality of the whole series of complexes despite f-compression and this result was confirmed by DFT calculations. Abstract: The search for efficient methods of comparative structural investigations of coordination compounds in solid state and solutions is a very relevant task. In this study, structural assignments in a series of Ln2 [(15C5)4 Pc]3 complexes (where [(15C5)4 Pc] 2- is 2, 3, 9, 10, 16, 17, 24, 25-tetrakis(15-crown-5)phthalocyaninato-dianion, Ln = Nd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+ and Tm 3+ ) was performed using NMR relaxation and paramagnetic lanthanide-induced shifts (LIS) data. Analysis of the paramagnetic chemical shifts and relaxation rates evidenced of isostructurality of the complete series of the investigated triple-decker complexes in the solutions. The performed systematic DFT calculations for a series of model complexes with methoxy-substituted ligands Ln2 [(MeO)8 Pc]3 demonstrate that the calculated geometrical factors are in agreement with characteristics extracted from experimental NMR data.