Yuan Shang-Fu, Lei Zhen, Guan Zong-Jie, Wang Quan-Ming
Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, 100084, P. R. China.
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2021 Mar 1;60(10):5225-5229. doi: 10.1002/anie.202012499. Epub 2021 Jan 19.
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 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 (Ph P) (dpa) Cl](SO CF ) (Au , dpa=dipyridylamido) has been successfully synthesized. Single crystal structural determination reveals that Au 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.
具有表面开放位点的金纳米团簇对于催化领域的实际应用至关重要。我们通过使用不同位阻类型的混合配体开发了一种表面几何失配策略。当同时使用体积较大的膦Ph P和平面二吡啶胺（Hdpa）时，配体之间的空间排斥会降低金团簇的配体覆盖率。已成功合成了一种结构明确的可接近金纳米团簇[Au (Ph P) (dpa) Cl](SO CF )（Au ，dpa = 二吡啶酰胺基）。单晶结构测定表明，Au具有八个呈扭曲双帽三棱柱形状的未配位金原子。通过用2-萘硫醇进行发光滴定定量证实了暴露的Au原子的可及性。该团簇在将苯甲醇选择性氧化为苯甲醛方面具有优异的性能，并且由于带负电荷的多齿配体dpa的保护而表现出优异的稳定性。
