Illuminating spin-crossover octanuclear metal-organic cages  

作　　者：Zhi-Kun Liu Alyona A.Starikova Yu-Xia Li Ke Sun Meng Yu Zi-Shuo Yao Jun Tao 

机构地区：[1]Key Laboratory of Cluster Science of Ministry of Education,School of Chemistry and Chemical Engineering,Liangxiang Campus,Beijing Institute of Technology,Beijing 102488,China [2]Institute of Physical and Organic Chemistry,Southern Federal University,Rostov-on-Don 344090,Russia

出　　处：《Science China Chemistry》2024年第4期1208-1215,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(92061106,22101021,22071009);the Ministry of Science and Higher Education of the Russian Federation(State assignment in the field of scientific activity,project No.FENW-2023-0017)。

摘　　要：Spin-crossover(SCO)materials that reversibly switch between high-and low-spin states have potential for the storage of spin state-relative information,and have gained much attention incorporating secondary physical properties,such as fluorescence and magneto-optical switching.In this study,we synthesized three octanuclear metal-organic cages(MOCs)using tetraphenylethylene-based luminophores,aldehydes,and Fe^(Ⅱ)salts,by subcomponent self-assembly approach,namely[Fe1]-[Fe3].By controlling the ligand-field strength and guest encapsulation,we finely tuned their SCO properties.Among them,MOC[Fe2]displayed nearly complete SCO behavior in the solid state,which is rare for high-nuclearity complexes.We also demonstrated the coupling of SCO with fluorescence emission in these MOCs by using isostructural Zn^(Ⅱ)complexes([Zn1]-[Zn3])as control experiments,for the first time.Theoretical calculations revealed the energy-transfer mechanism between fluorophores and SCOactive centers,which emphasizes the significant contribution of d-d transitions in the interplay between the occurrence of SCO and fluorescence emission.

关 键 词：metal-organic cages spin crossover FLUORESCENCE switching materials DFT calculation 

分 类 号：O641.4[理学—物理化学]