[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core

被引:86
作者
Lee, Sanghwa [5 ,6 ,7 ]
Bootharaju, Megalamane S. [5 ,6 ,7 ]
Deng, Guocheng [3 ,4 ]
Malola, Sami [1 ,2 ]
Baek, Woonhyuk [5 ,6 ,7 ]
Hakkinen, Hannu [1 ,2 ]
Zheng, Nanfeng [3 ,4 ]
Hyeon, Taeghwan [5 ,6 ,7 ]
机构
[1] Univ Jyvaskyla, Nanosci Ctr, Dept Phys, FI-40014 Jyvaskyla, Finland
[2] Univ Jyvaskyla, Nanosci Ctr, Dept Chem, FI-40014 Jyvaskyla, Finland
[3] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Suifaces, Collaborat Innovat Ctr Chem Energy Mat, Xiamen 361005, Peoples R China
[4] Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China
[5] Inst Basic Sci IBS, Ctr Nanoparticle Res, Seoul 08826, South Korea
[6] Seoul Natl Univ, Sch Chem & Biol Engn, Seoul 08826, South Korea
[7] Seoul Natl Univ, Inst Chem Proc, Seoul 08826, South Korea
基金
芬兰科学院; 中国国家自然科学基金;
关键词
METAL NANOCLUSTERS; GOLD NANOCLUSTERS; CLUSTERS; NANOPARTICLES;
D O I
10.1021/jacs.0c06577
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu-32(PET)(24)H8Cl2](PPh4)(2) coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antiprismatic Cu14H8 core, assembled by two square antiprisms by edge sharing, followed by hydride binding. The rod-shaped Cu14H8 core is clamped by two complex Cu-7(PET)(11)Cl and two simple Cu2PET metal ligand frameworks, constructing the complete structure of Cu-32 NC. The presence, number, and location of hydrides are established by combined experimental and density functional theory results. The electronic structure calculations show the cluster as a zero-free-electron system, reproduce well the measured optical absorption spectrum, and explain the main absorption features. Furthermore, the Cu-32 cluster is found to be a highly active homogeneous catalyst for C-N bond formation in aniline carbonylation reactions at room temperature. We hope that new findings in this work will stimulate and expand the research on Cu and other active metal NCs.
引用
收藏
页码:13974 / 13981
页数:8
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