Lara Garnica Rebeca, Rama Raquel J, Chambrier Isabelle, Agonigi Gabriele, Hughes David L, Lalinde Elena, Bochmann Manfred, Fernandez-Cestau Julio
School of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ, U.K.
Departamento de Química─Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, E-26006 Logroño, Spain.
Inorg Chem. 2023 Aug 14;62(32):12683-12696. doi: 10.1021/acs.inorgchem.3c00870. Epub 2023 Aug 3.
The syntheses and structures of a series of complexes based on the CC-chelated Au(III) unit (CC = 4,4'-bis(-butyl) 2,2'-biphenyl-1,1'-diyl) are reported, namely, [{(CC)Au(C≡CBu)}M], (CC)Au(C≡CR)(C≡NXyl), and [{(CC)Au(C≡CR)}{M(C≡NXyl)}] (M = Ag, Cu; R = Bu, CHBu-4, CHOMe-4; Xyl = 3,5-MeCH). The X-ray structures reveal a broad range of dispositions determined by the different coordination modes of Ag(I) or Cu(I). The complexes are bright photoemitters in the solid state and in poly(methyl methacrylate) (PMMA) films. The photoluminescence is dominated by IL(CC) transitions, with indirect effects from the rest of the molecules, as supported by theoretical calculations. This work opens up the possibility of accessing Au(III) carbon-rich anions to construct photoluminescent aggregates.
报道了一系列基于CC螯合金（III）单元（CC = 4,4'-双（-丁基）2,2'-联苯-1,1'-二基）的配合物的合成及其结构，即[{(CC)Au(C≡CBu)}M]、(CC)Au(C≡CR)(C≡NXyl)和[{(CC)Au(C≡CR)}{M(C≡NXyl)}]（M = Ag、Cu；R = Bu、CHBu-4、CHOMe-4；Xyl = 3,5-MeCH）。X射线结构揭示了由Ag（I）或Cu（I）的不同配位模式所决定的广泛排列方式。这些配合物在固态和聚甲基丙烯酸甲酯（PMMA）薄膜中均为明亮的光发射体。光致发光以IL(CC)跃迁为主，理论计算表明其余分子存在间接影响。这项工作开启了获取富含金（III）碳阴离子以构建光致发光聚集体的可能性。
