Mononuclear Fe(iii) complexes with 2,4-dichloro-6-((quinoline-8-ylimino)methyl)phenolate: synthesis, structure, and magnetic behavior

Abstract

Three Fe(iii)-based coordination complexes [Fe(dqmp)2](NO3)·H2O (1), [Fe(dqmp)2](BF4)·2CH3COCH3 (2), and [Fe(dqmp)2](ClO4) (3) were synthesized from Fe(NO3)3·9H2O/Fe(ClO4)3·xH2O, NaBF4, and 2,4-dichloro-6-((quinoline-8-ylimino)methyl)phenol (Hdqmp) in methanol/acetone and characterized. The structures of complexes 1-3 were determined via single-crystal X-ray crystallography at 100 K and room temperature, and their magnetic properties in the solid and solution forms were investigated. All complexes showed meridional structures with two tridentate dqmp− ligands coordinated with Fe(iii) cations. In the solid state, complex 1 showed an abrupt and complete spin crossover at 225 K, whereas complexes 2 and 3 exhibited an incomplete spin crossover at 135 and 150 K, respectively. In a dimethylformamide solution, the complexes showed counterion-dependent spin transitions. In contrast to the solid state, in solution, complex 1 did not exhibit complete spin crossover. However, complexes 2 and 3 showed more complete spin transitions in solutions than in the solid state. The relaxation times, T1 and T2, for 1 and 2 were determined and both increased with temperature from 220 to 380 K. The T1 of 1 was larger than that of 2 at 380 K, and the T1 values were larger than the T2 values.