Atomically Precise Preorganization of Open Metal Sites on Gold Nanoclusters with High Catalytic Performance

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 Ph3P and planar dipyridyl amine (Hdpa) are simultaneously used, steric re...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 60; no. 10; pp. 5225 - 5229
Main Authors Yuan, Shang‐Fu, Lei, Zhen, Guan, Zong‐Jie, Wang, Quan‐Ming
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 01.03.2021
EditionInternational ed. in English
Subjects
amine ligands
Benzaldehyde
Benzyl alcohol
Catalysis
cluster compounds
Crystal structure
Gold
Ligands
luminescent titration
Nanoclusters
Oxidation
Phosphine
Phosphines
selective oxidation
Single crystals
Titration
gold
cluster compounds
luminescent titration
amine ligands
selective oxidation
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Summary: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 Ph3P 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 [Au23(Ph3P)10(dpa)2Cl](SO3CF3)2 (Au23, dpa=dipyridylamido) has been successfully synthesized. Single crystal structural determination reveals that Au23 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. A stable Au23 nanocluster with preorganized open sites has been conducted through surface geometric mismatch strategy. The 35 % accessibility of Au23 was confirmed by luminescent titration with 2‐naphthalenethiol. The preorganized open sites make intact Au23 a high‐performance catalyst for aerobic oxidation of benzyl alcohol.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202012499