Luminescent Chains Formed from Neutral, Triangular Gold Complexes Sandwiching Tl<sup>I</sup> and Ag<sup>I</sup>. Structures of {Ag([Au(μ-C<sup>2</sup>,N<sup>3</sup>-bzim)]<sub>3</sub>)<sub>2</sub>}BF<sub>4</sub>·CH<sub>2</sub>Cl<sub>2</sub>, {Tl([Au(μ-C<sup>2</sup>,N<sup>3</sup>-bzim)]<sub>3</sub>)<sub>2</sub>}PF<sub>6</sub>·0.5THF (bzim = 1-Benzylimidazolate), and {Tl([Au(μ-C(OEt)NC<sub>6</sub>H<sub>4</sub>CH<sub>3</sub>)]<sub>3</sub>)<sub>2</sub>}PF<sub>6</sub>·THF, with MAu<sub>6</sub> (M = Ag<sup>+</sup>, Tl<sup>+</sup>) Cluster Cores
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It has been found that several trinuclear complexes of AuI interact with silver and thallium salts to intercalate Ag+ and Tl+ cations, thereby forming chains. The resulting sandwich clusters center the cations between the planar trinuclear moieties producing structures in which six AuI atoms interact with each cation in a distorted trigonal prismatic coordination. The resultant (B3AB3B3AB3)∞ pattern of metal atoms also shows short (∼3.0 Å) aurophilic interactions between BAB molecular centers. These compounds display a strong visible luminescence, under UV excitation, which is sensitive to temperature and the metal ion interacting with the gold. X-ray crystal structures are reported for Ag([Au(μ-C2,N3-bzim)]3)2BF4·CH2Cl2 (P , Z = 2, a = 14.4505(1)Å; b = 15.098(2)Å; c = 15.957(1)Å; α = 106.189(3)°; β = 103.551(5)°; γ = 101.310(5)°); Tl([Au(μ-C2,N3-bzim)]3)2PF6·0.5C4H8O (P , Z = 2, a = 15.2093(1)Å; b =15.3931(4)Å; c = 16.1599(4)Å; α = 106.018(1)°; β = 101.585(2)°; γ=102.068(2)°); and Tl([Au(μ-C(OEt)NC6H4CH3)]3)2PF6·C4H8O (P2(1)/n, Z = 4, a = 16.4136(3)Å; b = 27.6277(4)Å; c = 16.7182(1)Å; β = 105.644(1)°). Each compound shows that the intercalated cation, Ag+ or Tl+, coordinates to a distorted trigonal prism of six AuI atoms. The counteranions reside well apart from the cations between the cluster chains.
研究发现，若干一价金(Au(I))三核配合物可与银盐及铊盐作用，将Ag+与Tl+阳离子嵌入其中，进而形成链状结构。所得夹心簇将阳离子置于平面三核单元之间，形成如下结构：每个阳离子与六个一价金原子以畸变三角棱柱配位模式相互作用。所形成的金属原子排列模式(B3AB3B3AB3)∞同时展现出BAB分子单元之间的短程（~3.0 Å）亲金相互作用。此类化合物在紫外激发下展现出强烈的可见光发光，其发光性能对温度及与金作用的金属离子均具有敏感性。本文报道了三种化合物的X射线晶体结构：Ag([Au(μ-C2,N3-bzim)]3)2BF4·CH2Cl2（空间群P，Z=2，晶胞参数a=14.4505(1)Å；b=15.098(2)Å；c=15.957(1)Å；α=106.189(3)°；β=103.551(5)°；γ=101.310(5)°）；Tl([Au(μ-C2,N3-bzim)]3)2PF6·0.5C4H8O（空间群P，Z=2，晶胞参数a=15.2093(1)Å；b=15.3931(4)Å；c=16.1599(4)Å；α=106.018(1)°；β=101.585(2)°；γ=102.068(2)°）；以及Tl([Au(μ-C(OEt)=NC6H4CH3)]3)2PF6·C4H8O（空间群P2(1)/n，Z=4，晶胞参数a=16.4136(3)Å；b=27.6277(4)Å；c=16.7182(1)Å；β=105.644(1)°）。所有化合物均证实，嵌入的阳离子Ag+或Tl+与六个一价金原子构成的畸变三角棱柱配位。抗衡阴离子位于簇状链之间，与阳离子相距较远。
