Department of Chemistry, The University of Western Ontario , London, Ontario N6A 5B7, Canada.
Institut für Nanotechnologie, Karlsruher Institut für Technologie , Hermann-von Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
J Am Chem Soc. 2017 Oct 11;139(40):14045-14048. doi: 10.1021/jacs.7b09025. Epub 2017 Sep 27.
A new class of coinage-metal chalcogenide compounds [AuM(μ-E)(IPr)] (M = Ag, Au; E = S, Se, Te) has been synthesized from the combination of N-heterocyclic carbene-ligated gold(I) trimethylsilylchalcogenolates [(IPr)AuESiMe] 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 → AuM) 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.
一类新型的金属-硫属元素（E=S、Se、Te）配位化合物[AuM(μ-E)(IPr)]（M=Ag、Au）已通过 N-杂环卡宾配位的金（I）三甲基硅基硫属化合物[(IPr)AuESiMe]与配体支持的金属乙酸盐的组合合成得到。这些簇合物在 2-甲基四氢呋喃的玻璃态和 77 K 的固态中观察到磷光，其发射能取决于金属/硫属离子组成的选择。通过时间相关密度泛函理论计算，发现这种调节发射的能力归因于混合配体到金属-金属-电荷转移（IPr→AuM）和配体间（IPr→E）磷光特性的电子跃迁。N-杂环卡宾（NHCs）已被应用于发光金（I）硫属化物簇合物的合成中作为辅助配体，这种方法允许在稳定的八核框架内对存在的金属和硫属离子进行前所未有的选择性。
