Luminescent supramolecular gold

This topic will be divided into two parts according to the heterometal interacting with gold the first will focus on the luminescent supramolecular structures that contain gold and other coinage elements the second will examine those containing gold and other heterometals. 

Of the metals that form luminescent supramolecular entities with gold, that for which most complexes are known is thallium in its +1 oxidation state. As described below, in recent years the contributions of several laboratories have been reported. Nevertheless, in some cases, the papers also report similar reactions with other metals, leading to similar structures. In order to maintain a congruent synthetic description, those examples will be discussed together as they appear in the original work. 

The first descriptions of heteronuclear luminescent supramolecular complexes were given by Fackler et al. in 1988 and 1989. In these studies, one gold-thallium and one gold-lead complex were reported. As in the case of the gold-silver dinuclear systems, the extended systems appeared as a result of the unidirectional polymerization of dinuclear or trinuclear units through metal-metal interactions. These were prepared by reaction of the gold precursor [PPN][Au(MTP)2] (PPN = N(PPh3)2 ... 

As described above, among the several closed-shell metal ions that form luminescent supramolecular entities with gold, thallium(I) forms the most numerous examples. While aurophilic attractions can be considered the upper extreme of the metallophilic interactions (with values up to 46 kJ mol-1), intermetallic contacts involving T1(I) centers appear as the weakest ones (even <20 kJ mol-1),46 which is explained by the enhancement of the Au---Au interactions and the weakening of the Van der Waals attractions between the s2 metal atoms produced by the relativistic effects.47 Nevertheless, the complexes in which this interaction appears are surprisingly stable, with additional electrostatic, packing forces, or the ligand architecture, responsible for this fact. 

As far as we know, the only example of a supramolecular gold-lead complex described that exhibits luminescence was reported by Fackler s laboratory in 1989. 

N(C6H4-p-Me)Au[3 to aggregate through gold-gold intermolecular interactions forming these supramolecular arrays confers to its extraordinary luminescent properties which have been described by Balch as solvoluminescence [48]. 

Fernandez, F.J., Jones, P.G., Laguna, A., Lopez-de-Luzuriaga, J.M., Monge, M., Perez, J. and Olmos, M.E. (2002) Synthesis, Structure, and Photophysical Studies of Luminescent Two- and Three-Dimensional Gold-Thallium Supramolecular Arrays. Inorganic Chemistry, 41(5), 1056-1063. 

Vickery, J.C., Olmstead, M.M., Fung, E.Y. and Balch, A.L. (1997) Solvent-stimulated luminescence from the supramolecular aggregation of a trinuclear gold(I) complex that displays extensive intermolecular Au Au interactions. Angewandte Chemie, 109, 1227-1229 (1997) Angewandte Chemie (International Edition in English), 36, 1179-1181. 

Coco, S., Cordobilla, C., Dominguez, C. and Espinet, P. (2008) Luminescent gold(I) metallo-adds and their hydrogen bonded supramolecular liquid crystalline derivative s with decyloxystilbazole as hydrogen acceptor. Dalton Transactions, 48,6894—6900. 

Charge-transfer adducts are formed with the gold(I) trimers [Au3(MeN=COR)3] (R = Me, Et), which act as electron donors, and organic electron acceptors as nitro-9-fluorenes. The structures of these adducts involve mixed stacks in which the gold trimers and the planar nitro-fluorenes are interleaved.3130 No luminescence has been observed from these solid charge-transfer adducts, which is not surprising since the luminescence of [Au3(MeN=COR)3] is a property that is associated with the supramolecular organization in the solid. 

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