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Report No.

On/off spin-crossover phenomenon and control of the transition temperature in assembled Iron(II) complexes

Nakashima, Satoru*; Kaneko, Masashi ; Yoshinami, Keisuke*; Iwai, Saki*; Dote, Haruka*

The present study reveals the on/off of spin-crossover (SCO) phenomenon in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand. Whether SCO phenomenon occurs or not in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand is determined by local structure around iron atom. SCO phenomenon occurs when the coordinating pyridines facing to each other across the iron atom are propeller type, while the phenomenon does not occur when they are parallel type or distorted propeller type. DFT calculation explained that, in the shortening of Fe-pyridine bonds when changing from high-spin state to low-spin state, the pyridines of propeller type can approach the iron atom with smaller steric hindrance than those of parallel and distorted propeller type complexes. The local structure is controlled by introducing methyl substituent and introducing $$pi$$-system, changing SCO phenomenon. And the transition temperature of SCO is also controlled in assembled complexes bridged by 1,2-bis(4-pyridyl)ethane by mixing anionic ligand.



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