Electronic Transition and Magnetic Coupling Regulation in Trimetallic Complexes Featuring a New Bridging Ligand...

A series of trimetallic complexes [Fe^III(μ-L)(py)]₂M^II(py) (n = 2, M^II = Mn^II, 1; Fe^II, 2; Co^II, 3; Zn^II, 4; n = 3, M^II = Cd^II, 5) with a new bridging ligand L^4- (deprotonated 1,2-N-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 L^4- coordinates to the terminal Fe^III ions (intermediate-spin with S_Fe = 3/2) by the N, S atoms, and coordinate to the central metal M^II 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 M^II changes from Fe^II to Co^II and Mn^II, while the paramagnetic behaviors are presented when M^II = Zn^II and Cd^II, confirmed by the magnetic susceptibility measurements and further supported by using the PHI program. Furthermore, the bridging ligand to the terminal Fe^III charge transfer (LMCT) transitions emerged in all complexes but the central Fe^II to terminal Fe^III charge transfer (MMCT) only presented in complex 2, strongly supported by the UV/vis-NIR electronic spectra and TDDFT calculations.