Halogen‐Driven Single‐Crystal to Single‐Crystal Transformation Engineering the Cluster‐based Spin Crossover Frameworks
Cluster-based spin crossover (SCO) frameworks are a new class of smart metal-organic frameworks (MOFs) with diverse structures and topologies and unique bistable physicochemical properties. Here, we report a cluster-based SCO framework [Fe<sub>3</sub>{Ag<sub>4</sub>(CN)<sub>6</sub>(H<sub>2</sub>O)}<sub>2</sub>(TPBA)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> ⋅ 7DMF (1) with an extremely rare 3,4,6-T108 topology, in which the tripodal [Ag{Ag(CN)<sub>2</sub>}<sub>3</sub>(H<sub>2</sub>O)]<sup>2-</sup> clusters axially link the Fe<sup>2+</sup> ions to form 2D→3D n-fold Borromean entangled networks. Under the guidance of reticular chemistry, the post-synthetic modification (PSM) from 1 with 3,4,6-T108 topology to [Fe<sub>3</sub>{Ag<sub>8</sub>X<sub>8</sub>(CN)<sub>6</sub>}(TPBA)<sub>3</sub>] (2_X, X=Cl, Br, I) with urk topology is firstly achieved via single-crystal to single-crystal (SCSC) transformation. Moreover, the successive SCSC transformations from 2_Cl to 2_Br and then to 2_I are realized for the first time. Their SCO behaviors are also modified by halogen-driven stepwise cluster transformations. Hence, these findings provide new strategies for the development of cluster-based SCO MOFs towards the smart functional porous materials.
Authors
- Si‐Guo Wu (ORCID: https://orcid.org/0000-0002-0110-8350)
- Ze‐Yu Ruan (ORCID: https://orcid.org/0000-0003-0447-7626)
- Guang Yang (ORCID: https://orcid.org/0000-0002-1379-0684)
- Pei-Yu Liao
- Yan-Cong Chen
- Zhao-Ping Ni
Institutions
- Sun Yat-sen University (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-10-11
- DOI
- https://doi.org/10.1002/anie.202414330
- Citations
- 3
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.35