Synthesis, Structure, and Luminescent Behavior of Anionic Oligomeric and Polymeric Ag2Au2 Clusters

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• 作者：Nicky Savjani ; Luke A. Wilkinson ; David L. Hughes ; Mark Schormann ; Manfred Bochmann
• 刊名：Organometallics
• 出版年：2012
• 出版时间：November 12, 2012
• 年：2012
• 卷：31
• 期：21
• 页码：7600-7609
• 全文大小：643K
• 年卷期：v.31,no.21(November 12, 2012)
• ISSN：1520-6041

文摘

Mixtures of silver salts AgX (X = NO₃, CF₃CO₂, CF₃SO₃) with M[Au(C₆F₅)₂] (M = NBu₄, PPh₄) gave respectively the ionic mixed-metal clusters [M₂{(C₆F₅)₄Au₂Ag₂X₂}]_n (1, X = NO₃; a, M = NBu₄; b, M = PPh₄) and [M{(C₆F₅)₄Au₂Ag₂X}]_n, (2a,b, X = CF₃CO₂; 3a,b, X = CF₃SO₃). The degree of aggregation n of these cluster compounds depends strongly on the method of isolation (solvent evaporation or precipitation); for example, recrystallization of 1a gave a crystalline salt of the tetraanion [(C₆F₅)₄Au₂Ag₂X₂]₂^{4鈥?/sup> as well as the polymer [(NBu₄)₂{(C₆F₅)₄Au₂Ag₂(NO₃)₂}]_n. The aurophilic Au路路路Au interactions strongly influence the photoemission wavelength. The anion X has remarkably little effect on the luminescence color but strongly influences the conformation of the polyanionic chains, leading to a variety of solid-state structures, from well-defined dimers (1a1) to linear (1b) and curved (1a2, 2a) polymeric chain aggregates.}