A N-Heterocyclic Carbene-Stabilized Coinage Metal-Chalcogenide Framework with Tunable Optical Properties

被引:64
作者
Polgar, Alexander M. [1 ]
Weigend, Florian [2 ,3 ]
Zhang, Angel [1 ]
Stillman, Martin J. [1 ]
Corrigan, John F. [1 ,4 ]
机构
[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada
[2] Karlsruher Inst Technol, Inst Nanotechnol, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany
[3] Karlsruher Inst Technol, Inst Phys Chem, Kaiserstr 12, D-76131 Karlsruhe, Germany
[4] Univ Western Ontario, Ctr Adv Mat & Biomat Res, London, ON N6A 3K7, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
SULFUR CENTERS. SYNTHESIS; AUROPHILIC INTERACTIONS; COMPLEXES; CRYSTAL; GOLD(I) SULFIDO; LUMINESCENCE; CLUSTER; LIGANDS; COPPER; PHOTOLUMINESCENCE; TRANSFORMATION;
D O I
10.1021/jacs.7b09025
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A new class of coinage-metal chalcogenide compounds [Au4M4(mu(3)-E)(4)(IPr)(4)] (M = Ag, Au; E = S, Se, Te) has been synthesized from the combination of N-hetero cyclic carbene-ligated gold(I) trimethylsilyl-chalcogenolates [(IPr)AuESiMe3] and ligand-supported metal acetates. Phosphorescence is observed from these clusters in glassy 2-methyltetrahydrofuran and in the solid state at 77 K, with emission energies that depend on the selection of metal/chalcogen ion composition. The ability to tune the emission is attributed to electronic transitions of mixed ligand-to-metal-metal-charge-transfer (IPr -> AuM2) and interligand (IPr -> E) phosphorescence character, as revealed by time-dependent density functional theory computations.N-heterocyclic carbenes (NHCs) have been applied as ancillary ligands in the synthesis of luminescent gold(I) chalcogenide clusters and this approach allows for unprecedented selectivity over the metal and chalcogen ions present within a stable octanuclear framework.
引用
收藏
页码:14045 / 14048
页数:4
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