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Atomically Precise Preorganization of Open Metal Sites on Gold Nanoclusters with High Catalytic Performance
Author(s) -
Yuan ShangFu,
Lei Zhen,
Guan ZongJie,
Wang QuanMing
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202012499
Subject(s) - nanoclusters , chemistry , denticity , ligand (biochemistry) , catalysis , steric effects , phosphine , gold cluster , crystallography , cluster (spacecraft) , benzyl alcohol , metal , photochemistry , inorganic chemistry , crystal structure , stereochemistry , organic chemistry , computational chemistry , density functional theory , biochemistry , receptor , computer science , programming language
Abstract Gold nanoclusters with surface open sites are crucial for practical applications in catalysis. We have developed a surface geometric mismatch strategy by using mixed ligands of different type of hindrance. When bulky phosphine Ph 3 P and planar dipyridyl amine (Hdpa) are simultaneously used, steric repulsion between the ligands will reduce the ligand coverage of gold clusters. A well‐defined access granted gold nanocluster [Au 23 (Ph 3 P) 10 (dpa) 2 Cl](SO 3 CF 3 ) 2 ( Au 23 , dpa=dipyridylamido) has been successfully synthesized. Single crystal structural determination reveals that Au 23 has eight uncoordinated gold atoms in the shape of a distorted bicapped triangular prism. The accessibility of the exposed Au atoms has been confirmed quantitatively by luminescent titration with 2‐naphthalenethiol. This cluster has excellent performance toward selective oxidation of benzyl alcohol to benzaldehyde and demonstrates excellent stability due to the protection of negatively charged multidentate ligand dpa.