Spin-crossover phenomena of the mononuclear Mn(III) complex tuned by metal dithiolene counteranions

Ying Chen; Fan Cao; Rong-Min Wei; Yang Zhang; Yi-Quan Zhang; You Song

doi:10.1039/c3dt53173b

Spin-crossover phenomena of the mononuclear Mn(III) complex tuned by metal dithiolene counteranions

Dalton Trans. 2014 Mar 7;43(9):3783-91. doi: 10.1039/c3dt53173b.

Authors

Ying Chen¹, Fan Cao, Rong-Min Wei, Yang Zhang, Yi-Quan Zhang, You Song

Affiliation

¹ State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures and School of Chemistry and Chemical Engineering, Nanjing University, Hankou Road 22, Nanjing, 210093, P. R. China. yousong@nju.edu.cn.

PMID: 24441029
DOI: 10.1039/c3dt53173b

Abstract

Three ion-pair complexes based on spin-crossover [Mn(5-Br-sal-N-1,5,8,12)]ClO4 with TBA2[Ni(mnt)2], TBA2[Pt(mnt)2] (mnt = maleonitriledithiolate) and TBA[Ni(dmit)2] respectively (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) have been synthesized and structurally characterized. Complexes [Mn(5-Br-sal-N-1,5,8,12)]2[Ni(mnt)2] and [Mn(5-Br-sal-N-1,5,8,12)]2[Pt(mnt)2] are isomorphic and show the axial compression of the octahedral coordination environment of Mn(III) ions. With the temperature increasing the equatorial metal-ligand bond lengths show significant elongation, but the axial bond lengths remain unchanged. Complex [Mn(5-Br-sal-N-1,5,8,12)][Ni(dmit)2]·CH3CN contains π-π, p-π and H-bonds weak interactions. Magnetic investigation shows the spin-crossover phenomena for and , and T1/2 has been increased by 230 K comparing with the reactant complex. However, no spin-crossover was observed in complex , and theoretical calculations show that there are weak antiferromagnetic couplings mediated through π-π interactions.