Synthesis, structures and magnetic properties of polynuclear mixed-valence Mn(II)Mn(III) complexes containing 3-(2-phenol)-5-(pyridin-2-yl)-1,2,4-triazole ligand.

Abstract

This paper reports the synthesis, crystal structures, and magnetic properties of a series of mixed-valence polynuclear manganese complexes bridged by a dianionic 1,2,4-triazole-based ligand L(2-) (H(2)L = 3-(2-phenol)-5-(pyridin-2-yl)-1,2,4-triazole). Complexes 1 to 3 show a similar binuclear structure, with the central core of [Mn(II)Mn(III)(L)(2)] and some other small molecules also coordinated to the two Mn centers. The two [Mn(II)Mn(III)(L)(2)] subunits can be further connected by different dicarboxylic acids to construct non-charged tetranuclear complexes 4 to 7. In these complexes, each deprotonated dianionic ligand L(2-) acts as a mu(2)-bridged ligand to coordinate two Mn centers via the 1,2,4-triazole ring. Bond valence sum (BVS) calculations and Mn surrounding bond lengths indicate that the Mn center coordinated to the pyridine N atoms in the +2 oxidation state, while another Mn center coordinated to the phenolic O atoms is in the +3 oxidation state. The Mn(III) centre shows Jahn-Teller elongation along one of the axes. Magnetic studies show the presence of ferromagnetic Mn(III)-Mn(II) coupling in the binuclear (1-3) and tetranuclear (4-7) complexes with the magnetic coupling constant (J) ranging from 0.58 to 1.17 cm(-1), based on the Hamiltonian H = -2JS(1) x S(2) (S(1) = 5/2 and S(2) = 2). In all cases both z'J' (intermolecular interactions) and D parameter (Zero Field Splitting of the Mn (III) ion) has been introduced to improve the corresponding fit. The relationship of the coupling interaction between the Mn(II)/Mn(III) and their electronic structures is discussed.

DOI: 10.1039/b904553h

Cite this paper

@article{Liu2009SynthesisSA, title={Synthesis, structures and magnetic properties of polynuclear mixed-valence Mn(II)Mn(III) complexes containing 3-(2-phenol)-5-(pyridin-2-yl)-1,2,4-triazole ligand.}, author={Hui Liu and Jinlei Tian and Yingying Kou and Jingyan Zhang and Li Feng and Dongdong Li and Wen Gu and Xin Liu and Daizheng Liao and Peng Cheng and Joan de Pablo Ribas and Shiping Yan}, journal={Dalton transactions}, year={2009}, volume={47}, pages={10511-7} }