A Mixed-Valence {Fe13} Cluster Exhibiting Metal-to-Metal Charge-Transfer-Switched Spin Crossover |
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| Authors: | Wen Wen Dr. Yin-Shan Meng Dr. Cheng-Qi Jiao Qiang Liu Hai-Lang Zhu Prof. Ya-Ming Li Prof. Hiroki Oshio Prof. Tao Liu |
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| Affiliation: | State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Rd., 116024 Dalian, China |
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| Abstract: | 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 FeII-triazole moiety and generates a mixed-valence complex {[(Tp4-Me)FeIII(CN)3]9[FeII4(trz-ph)6]}⋅[Ph3PMe]2⋅[(Tp4-Me)FeIII(CN)3] ( 1 ; trz-ph=4-phenyl-4H-1,2,4-triazole). Moreover, MMCT occurs between FeIII and one of the FeII sites after heat treatment, resulting in the generation of a new phase, {[(Tp4-Me)FeII(CN)3][(Tp4-Me)FeIII(CN)3]8 [FeIIIFeII3(trz-ph)6]}⋅ [Ph3PMe]2⋅[(Tp4-Me)FeIII(CN)3] ( 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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| Keywords: | iron magnetism metal-to-metal charge transfer mixed-valence spin crossover |
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