Crystallographic Detection of the Spin State in FeIII Complexes

We report a single example of thermal spin crossover in a series of FeIII complexes, [FeIII(R-sal2323)]+, which typically stabilize the low-spin (S = 1/2) state. Single-crystal X-ray diffraction analysis of 53 such complexes with varying “R” groups, charge-balancing anions, and/or lattice solvation confirms bond lengths in line with an S = 1/2 ground state, with only the [FeIII(4-OMe-sal2323)]­NO3 complex (1a) exhibiting longer bond lengths associated with a percentage of the spin sextet form at room temperature. Structural distortion parameters are investigated for the series. A magnetic susceptibility measurement of 1a reveals a gradual, incomplete transition, with T 1/2 = 265 K in the solid state, while Evans method NMR reveals that the sample persists in the low-spin form in solution at room temperature. Computational analysis of the spin state preferences for the cations [FeIII(4-OMe-sal2323)]+ and [FeIII(sal2323)]+ confirmed the energetic preference for the spin doublet form in both, and the thermal spin crossover in complex 1a is therefore attributed to perturbation of the crystal packing on warming.