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Supramolecular Luminescent Gold(I)−Copper(I) Complexes: Self-Assembly of the AuxCuy Clusters inside the [Au3(diphosphine)3]3+ Triangles

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posted on 20.10.2008, 00:00 authored by Igor O. Koshevoy, Antti J. Karttunen, Sergey P. Tunik, Matti Haukka, Stanislav I. Selivanov, Alexei S. Melnikov, Pavel Yu. Serdobintsev, Mikhail A. Khodorkovskiy, Tapani A. Pakkanen
The reactions between diphosphino−alkynyl gold complexes (PhC2Au)PPh2(C6H4)nPPh2(AuC2Ph) (n = 1, 2, 3) with Cu+ lead to formation of the heterometallic aggregates, the composition of which may be described by a general formula [{AuxCuy(C2Ph)2x}Au3{PPh2(C6H4)nPPh2}3]3+(yx) (n = 1, 2, 3; x = (n + 1)(n + 2)/2; y = n(n + 1)). These compounds display very similar structural patterns and consist of the [AuxCuy(C2Ph)2x]yx alkynyl clusters “wrapped” in the [Au3(diphosphine)3]3+ triangles. The complex for n = 1 was characterized crystallographically and spectrally, the larger ones (n = 2, 3) were investigated in detail by NMR spectroscopy. Their luminescence behavior has been studied, and a remarkably efficient emission with a maximum quantum yield of 0.92 (n = 1) has been detected. Photophysical experiments demonstrate that an increase of the size of the aggregates leads to a decrease in photostability and photoefficiency. Computational studies have been performed to provide additional insight into the structural and electronic properties of these supramolecular complexes. The theoretical results obtained are in good agreement with the experimental data, supporting the proposed structural motif. These studies also suggest that the observed efficient long-wavelength luminescence originates from metal-centered transitions within the heterometallic Au−Cu core.