Electronic Transition and Magnetic Coupling Regulation in Trimetallic Complexes Featuring a New Bridging Ligand Obtained by Oxidative Addition.

Abstract

A series of trimetallic complexes [FeIII(μ-L)(py)]2MII(py)n (n = 2, MII = MnII, 1; FeII, 2; CoII, 3; ZnII, 4; n = 3, MII = CdII, 5) with a new bridging ligand L4- (deprotonated 1,2-N1,N2-bis(2-mercaptoanil) oxalimidic acid) were synthesized and fully characterized by elemental analysis, single-crystal X-ray crystallography, IR, and Mössbauer spectra. Interestingly, the bridging ligand was obtained by oxidative addition of the (gma•)3- ligand from the mononuclear precursor Fe(gma)py (gma = glyoxal-bis(2-mercaptoanil)). In the obtained complexes, the bridging ligand L4- coordinates to the terminal FeIII ions (intermediate-spin with SFe = 3/2) by the N, S atoms, and coordinate to the central metal MII ion by the four O atoms. The resonance structure of the bridging ligand can be described as the two 4π-electron delocalized systems connected by one single-bond (C1-C2), which is different from the electronic structure of the precursor Fe(gma)py. Remarkably, the magnetic coupling interaction can be regulated through the central metal. The ferromagnetic coupling constant J gradually decreases as MII changes from FeII to CoII and MnII, while the paramagnetic behaviors are presented when MII = ZnII and CdII, confirmed by the magnetic susceptibility measurements and further supported by using the PHI program. Furthermore, the bridging ligand to the terminal FeIII charge transfer (LMCT) transitions emerged in all complexes but the central FeII to terminal FeIII charge transfer (MMCT) only presented in complex 2, strongly supported by the UV/vis-NIR electronic spectra and TDDFT calculations.