Synthesis, characterization and structural analysis of complexes from 2,2':6',2''-terpyridine derivatives with transition metals

Acta Crystallogr C Struct Chem. 2024 Jun 1;80(Pt 6):200-211. doi: 10.1107/S2053229624004224. Epub 2024 May 16.

Abstract

The synthesis and structural characterization of three families of coordination complexes synthesized from 4'-phenyl-2,2':6',2''-terpyridine (8, Ph-TPY), 4'-(4-chlorophenyl)-2,2':6',2''-terpyridine (9, ClPh-TPY) and 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine (10, MeOPh-TPY) ligands with the divalent metals Co2+, Fe2+, Mn2+ and Ni2+ are reported. The compounds were synthesized from a 1:2 mixture of the metal and ligand, resulting in a series of complexes with the general formula [M(R-TPY)2](ClO4)2 (where M = Co2+, Fe2+, Mn2+ and Ni2+, and R-TPY = Ph-TPY, ClPh-TPY and MeOPh-TPY). The general formula and structural and supramolecular features were determinated by single-crystal X-ray diffraction for bis(4'-phenyl-2,2':6',2''-terpyridine)nickel(II) bis(perchlorate), [Ni(C21H15N3)2](ClO4)2 or [Ni(Ph-TPY)2](ClO4)2, bis[4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine]manganese(II) bis(perchlorate), [Mn(C22H17N3O)2](ClO4)2 or [Mn(MeOPh-TPY)2](ClO4)2, and bis(4'-phenyl-2,2':6',2''-terpyridine)manganese(II) bis(perchlorate), [Mn(C21H15N3)2](ClO4)2 or [Mn(Ph-TPY)2](ClO4)2. In all three cases, the complexes present distorted octahedral coordination polyhedra and the crystal packing is determined mainly by weak C-H...π interactions. All the compounds (except for the Ni derivatives, for which FT-IR, UV-Vis and thermal analysis are reported) were fully characterized by spectroscopic (FT-IR, UV-Vis and NMR spectroscopy) and thermal (TGA-DSC, thermogravimetric analysis-differential scanning calorimetry) methods.

Keywords: chelate complex; coordination chemistry; crystal structure; pincer ligand; supramolecular analysis; terpyridine.