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^II‐triazole moiety and generates a mixed‐valence complex {[(Tp^4‐Me)Fe^III(CN)₃]₉[Fe^II₄(trz‐ph)₆]}⋅[Ph₃PMe]₂⋅[(Tp^4‐Me)Fe^III(CN)₃] (1; trz‐ph=4‐phenyl‐4H‐1,2,4‐triazole). Moreover, MMCT occurs between Fe^III and one of the Fe^II sites after heat treatment, resulting in the generation of a new phase, {[(Tp^4‐Me)Fe^II(CN)₃][(Tp^4‐Me)Fe^III(CN)₃]₈ [Fe^IIIFe^II₃(trz‐ph)₆]}⋅ [Ph₃PMe]₂⋅[(Tp^4‐Me)Fe^III(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.

中文翻译：

---

混合价{Fe13}团簇，具有金属间电荷转移自旋交叉的特性。

利用金属间电荷转移（MMCT）和自旋交叉（SCO）来调节金属离子的化合价和自旋态，操纵材料的电子结构和功能是充满希望和挑战的。在本文中，金属氰酸盐构件用于与Fe ^II-三唑部分连接并生成混合价络合物{[（Tp ^4-Me）Fe ^III（CN）₃ ] ₉ [Fe ^II ₄（trz-ph）₆ ]}⋅[PH ₃ PME] ₂ ⋅[（TP ^4-ME）的Fe ^III（CN）₃ ]（1 ; TRZ-PH = 4-苯基-4- ħ-1,2,4-三唑）。此外，MMCT发生在热处理后的Fe ^III和一个Fe ^II位点之间，导致生成新相{{（Tp ^4-Me）Fe ^II（CN）₃ ] [（Tp ^4-Me）Fe ^III（CN）₃ ] ₈的[Fe ^III的Fe ^II ₃（TRZ-PH）₆ ]}⋅[PH ₃ PME] ₂ ⋅[（TP ^4-ME）的Fe ^III（CN）₃ ]（1）。结构和磁学研究表明MMCT可以调整1的两步SCO行为进入1 a的单步SCO行为。我们的工作表明，MMCT和SCO的集成可以为操纵具有可访问多电子态的功能性自旋转变材料提供新的选择。