Multi-step spin crossover accompanied by symmetry breaking in an Fe III complex: Crystallographic evidence and DFT studies

: Spin doctor: A mononuclear ferric complex [Fe(H-5-Br-thsa)(5-Br-thsa)]⋅H2O (1) (H2-5-Br-thsa = 5-bromo-2-hydroxybenzylidene)hydrazinecarbothioamide) was synthesized and its magnetic properties and structure were investigated by DFT calculations. This complex shows unprecedented reversible, six/five-step spin-crossover behavior accompanied by symmetry breaking. More importantly, each step in the multi-step transition was successfully characterized by single-crystal X-ray diffraction.