A dual-switching spin-crossover framework with redox regulation and guest response  

作　　者：Long-Fei Wang Si-Guo Wu Ze-Yu Ruan Ai-Qi Jian Wen Cui Zhao-Ping Ni Ming-Liang Tong 

机构地区：[1]Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China [2]CNRS,Centre de Recherche Paul Pascal,Pessac F-33600,France

出　　处：《Science China Chemistry》2023年第6期1744-1749,共6页中国科学（化学英文版）

基　　金：supported by the National Key Research and Development Program of China(2018YFA0306001);the National Natural Science Foundation of China(22075323);the Pearl River Talent Plan of Guangdong(2017BT01C161);the Guangdong Special Fund for Science and Technology Innovation Strategy(pdjh2023b0019);the Guangdong University Student Innovation Training Project(202210386)。

摘　　要：A dual-switching spin crossover metal-organic framework(SCO-MOF)[Fe(TPB){Pt^(Ⅱ)(CN)_(4)}]·3iPrOH·4H_(2)O(TPB=1,2,4,5-tetra(pyridin-4-yl)benzene)is developed via the combination of redox-active framework and tunable guests.The reversible structural transformation between[Pt^(Ⅱ)(CN)_(4)]^(2-) and[Pt^(Ⅳ)Br_(2)(CN)_(4)]^(2-)moieties can be manipulated by redox post-synthetic modification(PSM),which results in the change of SCO behaviors from step-wise to one-step.The influences of the oxidative addition of bromides on the ligand field splitting of Fe side are further explored by density functional theory calculations.Besides,the modulation of hysteretic four-/three-step,one-step and four-step SCO behaviors can be achieved by tuning the composition of guest molecules.Therefore,the combination of electronic bistability,redox reaction and guest recognition in a homogeneous lattice provides a utility platform for designing multi-responsive molecule-based materials.

关 键 词：spin crossover iron(Ⅱ) post-synthetic modification redox host-guest interaction 

分 类 号：TB34[一般工业技术—材料科学与工程]