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Issue 12, 2013
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Luminescent gold–silver complexes derived from neutral bis(perfluoroaryl)diphosphine gold(I) precursors

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Abstract

Complex [Au{4-C6F4(4-C6BrF4)}(tht)] reacts with diphosphines (L–L) such as bis(diphenylphosphino)methane (dppm) or 1,2-bis(diphenylphosphino)benzene (dppb) in a 2 : 1 molar ratio in dichloromethane, leading to neutral products of stoichiometry [(Au{4-C6F4(4-C6BrF4)})2(μ-L–L)] (L–L = dppm (1), dppb (2)). In the crystal structure of complex 2 short Au⋯Au interactions of 2.9367(5) and 2.9521(5) Å appear. This complex displays an orange emission, which is assigned to arise from a charge transfer transition from a metal centered Au–Au orbital to an orbital located at the diphosphine ligand. Addition of silver trifluoroacetate to these complexes in a 1 : 1 or a 2 : 1 molar ratio generates polymeric heterometallic gold–silver compounds of stoichiometry [Ag2Au2{4-C6F4(4-C6BrF4)}2(CF3CO2)2(μ-L–L)]n (L–L = dppm (3), dppb (4)), which confirms the capability of the neutral [(Au{4-C6F4(4-C6BrF4)})2(μ-diphosphine)] units to act as electron density donors when treated with a Lewis acid substrate. These heterometallic derivatives show blue emissions indicating large HOMO–LUMO band gaps, due to the stabilization that the gold-based HOMO orbitals suffer when the electron withdrawing silver trifluoroacetate fragments interact with them.

Graphical abstract: Luminescent gold–silver complexes derived from neutral bis(perfluoroaryl)diphosphine gold(i) precursors

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Publication details

The article was received on 20 Jul 2012, accepted on 18 Dec 2012 and first published on 18 Dec 2012


Article type: Paper
DOI: 10.1039/C2DT32973E
Citation: Dalton Trans., 2013,42, 4267-4277
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    Luminescent gold–silver complexes derived from neutral bis(perfluoroaryl)diphosphine gold(I) precursors

    R. V. Bojan, R. Czerwieniec, A. Laguna, T. Lasanta, J. M. López-de-Luzuriaga, M. Monge, M. E. Olmos and H. Yersin, Dalton Trans., 2013, 42, 4267
    DOI: 10.1039/C2DT32973E

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