1. Synthesis and Luminescence Properties of Two-Electron Bimetallic Cu-Ag and Cu-Au Nanoclusters via Copper Hydride Precursors
- Author
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Chun‐Yen Wu, Tzu-Hao Chiu, Ming-Hsi Chiang, Yu-Chiao Liu, Chi-Wei Yin, Yuan Jang Chen, Rhone P. Brocha Silalahi, Jean-Yves Saillard, Jhen-Heng Kao, Chen-Wei Liu, National Dong Hwa University (NDHU), Fu Jen Catholic University, Academica Sinica, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ministry of Science and Technology in Taiwan Ministry of Science and Technology, Taiwan [MOST 109-2113-M-259-008], France-Taiwan ANR-MOST program (project Nanoalloys), ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
chemistry.chemical_element ,Metal clusters ,[CHIM.INOR]Chemical Sciences/Inorganic chemistry ,010402 general chemistry ,Electrochemistry ,Ligands ,01 natural sciences ,Nanoclusters ,Inorganic Chemistry ,chemistry.chemical_compound ,Copper hydride ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,Dithiocarbamate ,Bimetallic strip ,chemistry.chemical_classification ,Cluster chemistry ,010405 organic chemistry ,Copper ,Hydrocarbons ,0104 chemical sciences ,Crystallography ,chemistry ,Phenylacetylene ,Gold ,Cyclic voltammetry - Abstract
International audience; The synthesis, structural characteristics, and photophysical properties of luminescent Cu-rich bimetallic superatomic clusters [Au@Cu-12((S2CNPr2)-Pr-n)(6)(C CPh)(4)](+) (1a(+)), [Au@Cu-12{S2P(OR)(2)}(6)(C CPh)(4)](+) (2(+)), (2a(+) = Pr-i; 2b(+) = Pr-n), [Au@Cu-12{S2P(C2H4Ph)(2)}(6)(C CPh)(4)](+) (2c(+)), and [Ag@Cu-12{S2P((OPr)-Pr-n)(2)}(6)(C CPh)(4)](+) (3(+)) were studied. Compositionally uniform clusters 1(+)-3(+) were isolated from the reaction of dithiolato-stabilized, polyhydrido copper clusters with phenylacetylene in the presence of heterometal salts. By using X-ray diffraction, the structures of 1a(+), 2a(+), 2b(+), and 3(+) were able to be determined. ESI-mass spectrometry and elemental analysis confirmed their compositions and purity. The structural characteristics of these clusters are similar with respect to displaying gold (or silver)-centered Cu-12 cuboctahedra surrounded by six dithiocarbamate/dithiophosph(in)ate and four alkynyl ligands. The doping of Au and Ag atoms into the polyhydrido copper nanoclusters significantly enhances their PL quantum yields from Ag@Cu-12 (0.58%) to Au@Cu-12 (55%) at ambient temperature in solution. In addition, the electrochemical properties of the new alloys were investigated by cyclic voltammetry.
- Published
- 2021