Modulation of Jahn-Teller distortion and electromechanical response in a Mn3+ spin crossover complex.

Structural, magnetic and electromechanical changes resulting from spin crossover between the spin quintet and spin triplet forms of a mononuclear Mn3+ complex embedded in six lattices with different charge balancing counterions are reported. Isostructural ClO4- and BF4- salts (1) and (2) each have two unique Mn3+ sites which follow different thermal evolution pathways resulting in a crossover from the spin quintet form at room temperature to a 1:1 spin triplet:quintet ratio below 150 K. The PF6- (3) and NO3- (4) salts which each have one unique Mn3+ site show a complete conversion from spin quintet to spin triplet over the same temperature range. A complete two step spin crossover is observed in the CF3SO3- lattice (5) with a 1:1 ratio of spin quintet and spin triplet forms at intermediate temperature, while the BPh4- lattice (6) stabilizes the spin triplet form over most of the temperature range with gradual and incomplete spin state switching above 250 K. An electromechanical piezoresponse was detected in NO3- complex 4 despite crystallization in a centrosymmetric space group. The role of deformations associated with stress-induced spin triplet-spin quintet switching in breaking the local symmetry are discussed and computational analysis is used to estimate the energy gap between the two spin states.