Hierarchical Homochiral Assembly of Polyhedral Cage-Type Nanoclusters  

作　　者：Cheng-Long Deng Bao-Liang Han Ze-Yu Liu Zhong-Hua Pan Jiao He Yu-Long Li Zhi-Lin Yang Geng-Geng Luo Chen-Ho Tung Di Sun Lan-Sun Zheng 

机构地区：[1]Key Laboratory of Environmentally Friendly Function Materials,Ministry of Education,College of Materials Science and Engineering,Huaqiao University,Xiamen 361021 [2]School of Chemistry and Chemical Engineering,State Key Laboratory of Crystal Materials,Shandong University,Ji’nan 250100 [3]College of Physical Science and Technology,Xiamen University,Xiamen 361005 [4]College of Chemistry and Environmental Engineering,Sichuan University of Science and Engineering,Zigong 643000 [5]State Key Laboratory for Physical Chemistry of Solid Surfaces,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005

出　　处：《CCS Chemistry》2024年第10期2537-2548,共12页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.22325105,92361301,52261135637,22171164,92161118,91961105,and 21641011);the Natural Science Foundation of Fujian Province(grant no.2022J01298);the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(grant no.SKLPEE-KF202109).

摘　　要：Hierarchical chiral self-assembly is of profound significance for biomolecules for their biological functions.Atom-precise metal nanoclusters(NCs)offer better opportunities to construct hierarchical superlattices.Nevertheless,achieving hierarchical homochiral assembly of nanocrystals protected by achiral ligands has proven to be a formidable task,with existing examples primarily limited to heterochiral assembly.Here we put forward a hierarchical assembly strategy towards precisely fabricating highly ordered homochiral superstructures.First,clusterin-nanocage type copper-hydride NCs act as synthons,of which entity is featured with a hexagonal close-packed Cu_(9)kernel embedded in a C_(3)-symmetric trigonal-prismatic metallacage,leading to a chiral core-shell primary structure with either P or M conformation.Then four homochiral NCs combined with guests through synergistic noncovalent interactions spontaneously organize into a supramolecular tetrahedral secondary structure within a unit cell.Finally,these nanoscopic supramolecular motifs pack into tertiary hierarchical superlattice of chiral cubic crystalline phase.Additionally,the crystalline material shows excellent robustness,and fascinating blueexcitable near-infrared thermally activated delayed fluorescence behavior.This work not only exhibits that nanocage-type NCs can be smart as proteins to translate chiral primary structure into tertiary chiral hierarchical complexity,but also provides new insights into structure-to-superstructure,enabling bottom-up creation of higher-level hierarchical homochiral superlattice structures.

关 键 词：polyhydrido copper nanoclusters chiral polyhedral metallacage hierarchical homochiral assembly thermally activated delayed fluorescence 

分 类 号：O62[理学—有机化学]