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

The synthesis and structural characterization of three families of coordination complexes synthesized from 40-phenyl-2,2':6',2''-terpyridine (8, Ph-TPY), 40-(4chlorophenyl)-2,2':6'2''-terpyridine (9, ClPh-TPY) and 40-(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(40-phenyl-2,20:60,200-terpyridine)nickel(II) bis(perchlorate), [Ni(C21H15N3)(2)](ClO4) (2) or [Ni(Ph-TPY)(2)](ClO4)(2), bis[40-(4-methoxyphenyl)-2,2'6',2''-terpyridine]manganese(II) bis(perchlorate), [Mn((C2H17N3O)-H-2)(2)](ClO4) (2) or [Mn(MeOPh-TPY)(2])(ClO4)(2), and bis(40-phenyl-2,2':6',2''-terpyridine)manganese(II) bis(perchlorate), [Mn(C21H15N3)2](ClO4) (2) or [Mn(PhTPY)(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.... 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.