Solid-state lattice effects on high-spin Mn(III) complexes with hexadentate Schiff-base ligand

This paper reports the syntheses, crystal structures, magnetics and spectroscopic properties of high-spin (HS) salts formula [Mn(salk-N-1,5,8,12)]Y·S (Y = AsF6 for 1, Y BF4, S CH3OH 2, PF6, 3), where (salk-N-1,5,8,12)2− (2,2ʹ-((2E,14E)-3,7,10,14-tetraazahexadeca-2,14-diene-2,15-diyl)diphenolate) is a hexadentate Schiff-base ligand. Crystal structural analysis indicates that extensive hydrogen bonds play primary role in stabilisation their HS states. As an aid to understanding this behaviour, structure known spin crossover compound [Mn(sal-N-1,5,8,12)]AsF6 (4) has been re-examined. To understand impact intermolecular forces different magnetic behaviours 1 4, we evaluate supramolecular structures confirm interactions can significantly affect cooperativity. Furthermore, electrochemical studies on 4 shows choice state controlled by solid-state lattice effects, i.e. cooperativity rather than molecular electronic effect.