Synthesis and characterization of iron clusters with an icosahedral[Fe@Fe_(12)]^(16+)Core  

作　　者：Gan Xu Yun-Shu Cui Xue-Lian Jiang Cong-Qiao Xu Jun Li Xu-Dong Chen 

机构地区：[1]Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China [2]Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry,Southern University of Science and Technology,Shenzhen 518055,China [3]Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education,Tsinghua University,Beijing 100084,China [4]State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing 210093,China

出　　处：《National Science Review》2024年第4期117-123,共7页国家科学评论（英文版）

基　　金：supported by the National Natural Science Foundation of China (92261107 and 22071110 to X.D.C., 22388102 and 22033005 to J.L., and 22103035 to C.Q.X.);the National Key Research and Development Program of China (2023YFA1506600,2022YFA1503900 and 2022YFA1503000);Guangdong Basic and Applied Basic Research Foundation (2020A1515110282 to C.Q.X.);Guangdong Provincial Key Laboratory of Catalysis (2020B121201002 to J.L.);financial support from the Priority Academic Program Development of Jiangsu Higher Educational Institutions,Jiangsu Collaborative Innovation Center of Biomedical Functional Materials,and State Key Laboratory of Coordination Chemistry in Nanjing University

摘　　要：Iron-metal clusters are crucial in a variety of critical biological and material systems,including metalloenzymes,catalysts,and magnetic storage devices.However,a synthetic high-nuclear iron cluster has been absent due to the extreme difficulty in stabilizing species with direct iron−iron bonding.In this work,we have synthesized,crystallized,and characterized a(Tp^(*))_(4)W_(4)S_(12)(Fe@Fe_(12))cluster(Tp^(*)=tris(3,5-dimethyl-1-pyrazolyl)borate(1−)),which features a rare trideca-nuclear,icosahedral[Fe@Fe_(12)]cluster core with direct multicenter iron−iron bonding between the interstitial iron(Fe_(i))and peripheral irons(Fe_(p)),as well as Fe_(p)…Fe_(p) ferromagnetic coupling.Quantum chemistry studies reveal that the stability of the cluster arises from the 18-electron shell-closing of the[Fe@Fe_(12)]^(16+)core,assisted by its bonding interactions with the peripheral tridentate[(Tp^(*))WS_(3)]^(4−)ligands which possess both S→Fe donation and spin-polarized Fe−Wσbonds.The ground-state electron spin is theoretically predicted to be S=32/2 for the cluster.The existence of low oxidation-state(OS∼+1.23)iron in this compound may find interesting applications in magnetic storage,spintronics,redox chemistry,and cluster catalysis.

关 键 词：Fe13 cluster iron-sulfur cluster low-valence iron iron−iron bond high spin complex 

分 类 号：O641.4[理学—物理化学]