Angew. Chem. ：含簇基单元的金属有机框架型自旋交叉材料

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探索新的结构体系是自旋交叉材料研究的永恒主题。自旋交叉配合物作为经典的磁双稳态材料，可在物理和化学刺激下实现高低自旋的可逆转变，因而在数据存储、分子开关、显色和传感等领域具有巨大的应用潜能。近年来，以金属团簇为节点的金属有机框架材料因其丰富的结构可调性、有趣的拓扑网络、超大的空腔和独特的物理化学性质而备受瞩目。然而，含簇基单元的金属有机框架型自旋交叉材料迄今尚未见报道。



1

近日，中山大学化学学院童明良教授和倪兆平副教授团队利用K[Ag(CN)2]、N,N,N',N'-四(吡啶-4-基)苯-1,4-二胺(TPBA)与FeX2 (X = Br和I)进行自组装，获得了两例同构的含{Ag8Br8(CN)6}簇的金属有机框架（MOF）材料[Fe3{Ag8Br8(CN)6}(TPBA)3]·9DMF (1)和[Fe3{Ag8I8(CN)6}(TPBA)3]·8DMF (2)。该框架MOF结构通过Fe(II)离子与六连接的 [Ag8X8(CN)6]6−簇和四连接的有机桥连配体TPBA间的配位作用形成罕见的I3O3型urk拓扑网络。二者均呈现出渐变型自旋交叉性质和自旋态依赖的荧光性质。

2

进一步地，配合物2可与LiTCNQ通过单晶到单晶转化的后合成反应，将{Ag8I8}团簇从其框架中摘除而转变为配合物3（[Fe(CN)2(TPBA)]·(KTCNQ)·2DMF·5.5H2O）。此时，在轴向上由氰根端基配位的低自旋亚铁离子作为四连接节点，与四连接的TPBA节点形成nbo拓扑网络。通过红外、电子自旋共振、扫描电子显微镜、能量色散谱仪和电喷雾电离质谱等手段证实了孔洞中存在KTCNQ客体。

3

在该工作中，中山大学团队成功合成了首例含簇基单元的金属有机框架型自旋交叉材料，利用单晶到单晶转化的后合成修饰策略实现了从urk到nbo拓扑的结构变化，有效调控了该材料的自旋态和荧光性质，为自旋交叉新体系的设计和后合成修饰提供了新的思路。

论文信息

Single-Crystal Transformation Engineering the Spin Change of Metal-Organic Frameworks via Cluster Deconstruction

Guang Yang, Si-Guo Wu, Ze-Yu Ruan, Yan-Cong Chen, Kai-Ping Xie, Zhao-Ping Ni* and Ming-Liang Tong*


Angewandte Chemie International Edition

DOI: 10.1002/anie.202312685

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