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A Mixed-Valence {Fe } Cluster Exhibiting Metal-to-Metal Charge-Transfer-Switched Spin Crossover. | LitMetric
It is promising and challenging to manipulate the electronic structures and functions of materials utilizing both metal-to-metal charge transfer (MMCT) and spin-crossover (SCO) to tune the valence and spin states of metal ions. Herein, a metallocyanate building block is used to link with a Fe -triazole moiety and generates a mixed-valence complex {[(Tp )Fe (CN) ] [Fe (trz-ph) ]}⋅[Ph PMe] ⋅[(Tp )Fe (CN) ] (1; trz-ph=4-phenyl-4H-1,2,4-triazole). Moreover, MMCT occurs between Fe and one of the Fe sites after heat treatment, resulting in the generation of a new phase, {[(Tp )Fe (CN) ][(Tp )Fe (CN) ] [Fe Fe (trz-ph) ]}⋅ [Ph PMe] ⋅[(Tp )Fe (CN) ] (1 a). Structural and magnetic studies reveal that MMCT can tune the two-step SCO behavior of 1 into one-step SCO behavior of 1 a. Our work demonstrates that the integration of MMCT and SCO can provide a new alternative for manipulating functional spin-transition materials with accessible multi-electronic states.
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