Sky-Blue Luminescent AuI鈥揂gI Alkynyl-Phosphine Clusters

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• 作者：Igor O. Koshevoy ; Antti J. Karttunen ; Ilya S. Kritchenkou ; Dmitrii V. Krupenya ; Stanislav I. Selivanov ; Alexei S. Melnikov ; Sergey P. Tunik ; Matti Haukka ; Tapani A. Pakkanen
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 1, 2013
• 年：2013
• 卷：52
• 期：7
• 页码：3663-3673
• 全文大小：579K
• 年卷期：v.52,no.7(April 1, 2013)
• ISSN：1520-510X

文摘

Treatment of the (AuC<sub>2sub>R)<sub>nsub> acetylides with phosphine ligand 1,4-bis(diphenylphosphino)butane (PbuP) and Ag<sup>+sup> ions results in self-assembly of the heterobimetallic clusters of three structural types depending on the nature of the alkynyl group. The hexadecanuclear complex [Au<sub>12sub>Ag<sub>4sub>(C<sub>2sub>R)<sub>12sub>(PbuP)<sub>6sub>]<sup>4+sup> (1) is formed for R = Ph, and the octanuclear species [Au<sub>6sub>Ag<sub>2sub>(C<sub>2sub>R)<sub>6sub>(PbuP)<sub>3sub>]<sup>2+sup> adopting two structural arrangements in the solid state were found for the aliphatic alkynes (R = Bu<sup>tsup> (2), 2-propanolyl (3), 1-cyclohexanolyl (4), diphenylmethanolyl (5), 2-borneolyl (6)). The structures of the compounds 1鈥?b>4 and 6 were determined by single crystal X-ray diffraction analysis. The NMR spectroscopic studies revealed complicated dynamic behavior of 1鈥?b>3 in solution. In particular, complexes 2 and 3 undergo reversible transformation, which involves slow interconversion of two isomeric forms. The luminescence behavior of the titled clusters has been studied. All the compounds exhibit efficient sky-blue room-temperature phosphorescence both in solution and in the solid state with maximum quantum yield of 76%. The theoretical DFT calculations of the electronic structures demonstrated the difference in photophysical properties of the compounds depending on their structural topology.