Luminescent Chains Formed from Neutral, Triangular Gold Complexes Sandwiching TlI and AgI. Structures of {Ag([Au(μ-C2,N3-bzim)]3)2}BF4·CH2Cl2, {Tl([Au(μ-C2,N3-bzim)]3)2}PF6·0.5THF (bzim = 1-Benzylimidazolate), and {Tl([Au(μ-C(OEt)═NC6H4CH3)]3)2}PF6·THF, with MAu6 (M = Ag+, Tl+) Cluster Cores | doi.page

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Luminescent Chains Formed from Neutral, Triangular Gold Complexes Sandwiching TlI and AgI. Structures of {Ag([Au(μ-C2,N3-bzim)]₃)₂}BF₄·CH₂Cl₂, {Tl([Au(μ-C2,N3-bzim)]₃)₂}PF₆·0.5THF (bzim = 1-Benzylimidazolate), and {Tl([Au(μ-C(OEt)═NC₆H₄CH₃)]₃)₂}PF₆·THF, with MAu₆ (M = Ag+, Tl+) Cluster Cores

Inorganic Chemistry2000Vol. 39(15), pp. 3158–3165

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Alfredo Burini, Rita Bravi, John P. Fackler, Rossana Galassi, Tiffany A. Grant, Mohammad A. Omary, Bianca Rosa Pietroni, Richard J. Staples

Abstract

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 [Formula: see text] , 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 [Formula: see text] , 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.

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Abstract

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