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Two-Dimensional Iron(II) Networks – Guest-Dependent Structures and Spin-Crossover Behaviors



Four compounds with general formula [Fe(4-bphz)2(NCS)2]·X [4-bphz = 1,2-bis(pyridin-4-ylmethylene)hydrazine; X = 2H2O·2CH3CN (CH3CN), 4CH3COCH3 (CH3COCH3), 2.5C10H8 (C10H8), 2C6H5NO2 (C6H5NO2)] were synthesized and characterized. These compounds contain 2D gridlike networks that are diversely stacked or self-interpenetrated depending on the inclusive guest molecules. Magnetic studies showed that CH3CN undergoes a two-step and almost complete spin transition and CH3COCH3 showed an incomplete transition, whereas C10H8 and C6H5NO2 are paramagnetic in the whole temperature range. Correlations between structures and magnetic properties revealed that the size and shape of the guest molecules exerted great influence on the conformation of the ligand and the 3D structures of the complexes and, hence, spin-crossover behaviors.