Citation: Guang Yang, Lu Yu, Ze-Yu Ruan, Ai-Qi Jian, Yan-Ru Chen, Yan-Cong Chen, Zhao-Ping Ni, Ming-Liang Tong. Self-assembly of spin crossover Fe(Ⅱ) framework materials with new topologies using tetra(pyridinyl)benzenediamine ligand[J]. Chinese Chemical Letters, ;2026, 37(10): 111656. doi: 10.1016/j.cclet.2025.111656 shu

Self-assembly of spin crossover Fe(Ⅱ) framework materials with new topologies using tetra(pyridinyl)benzenediamine ligand

Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, Sun Yat-sen University, Guangzhou 510275, China

nizhp@mail.sysu.edu.cn

tongml@mail.sysu.edu.cn

Received Date: 25 April 2025
Revised Date: 19 July 2025
Accepted Date: 30 July 2025
Available Online: 5 August 2025

Figures(5)

Spin crossover (SCO) metal-organic frameworks (MOFs) exhibit significant potential for applications in data storage, displays, switches, actuators and sensors. However, designing novel SCO MOFs with new framework topologies remains a considerable challenge. Herein, the self-assembly of FeBr₂ and Fe(ClO₄)₂·6H₂O with K[Ag(CN)₂] and N¹,N¹,N³,N³-tetra(pyridin-4-yl)benzene-1,3-diamine (i-TPBA) resulted in two distinct MOFs: [Fe^Ⅱ₃{Ag₈Br₈(CN)₆}(i-TPBA)₃]·4DEF (1, DEF = N,N-diethylformamide) and [Fe^Ⅱ{Ag(CN)₂}(i-TPBA)]ClO₄·2H₂O·0.5DEF (2). In 1, the hexatopic cluster anions [Ag₈Br₈(CN)₆]⁶⁻, tetratopic ligands i-TPBA and hexatopic Fe(Ⅱ) ions are linked to form a cluster-based MOF with the urk topology. In contrast, the [Ag(CN)₂]⁻ units in 2 axially bridge the Fe(Ⅱ) ions, constructing one-dimensional right-handed 3₁ helical chains, which are further linked by tetratopic i-TPBA connectors to generate a three-dimensional chiral framework with a previously unreported topology, designated as sco1. Moreover, the SCO behavior can be effectively modulated by thiophene guest molecules, leading to the observation of a rare scan rate-dependent hysteretic SCO behavior in 2_thio. Thus, this study demonstrates that multidentate ligands can be employed to construct SCO MOFs with new topologies, offering a versatile platform for the advancement of multifunctional SCO materials
- Spin crossover,
- Metal-organic framework,
- Cluster,
- Topology,
- Hysteresis
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