Au(I)-Tl(I): An Amazing Cooperative Couple

During the past few years, synthetic efforts have been addressed to the synthesis of polymeric materials with optical or semiconducting properties or even with capabilities to act as sensors for volatile organic compounds (1). The most recent studies have been concerned with the synthesis of heterometallic systems with short metal-metal interactions and the determination of their optical properties. These complexes are undoubtly interesting from a theoretical viewpoint and include an emerging class of luminescent materials, in which the observed luminescence results mainly from the interactions among the different metal centers, as well as the environments of these atoms. The understanding of the photophysics and photochemistry of these products could permit the design of complexes with appropriate metals and ligands chosen for individual applications. Following a synthetic strategy consisting on reactions between acid heterometal complexes and basic gold precursors we have succeded in synthesizing supramolecular assemblies formed via acid-base stacking, which display tunable luminescence or selective and reversible sensitivity to Vapour Organic Compounds (VOC?s) (2-5). In this sense, in accord with previous Mössbauer studies carried out in the gold precursor complex [AuR2]- (R = C6F5), the basic properties of this and related materials have been employed as building blocks of supramolecular assemblies in their reactions with complexes in wich the metallic centers act as lewis acids as, for instance, Tl(I) or Ag(I) (6). For instance, in the case of silver, by reacting equimolecular quantities of [NBu4][Au(C6F5)2] with AgClO4, in acetone, a solid of stoichiometry [Au2Ag2(C6F5)4(OCMe2)2]n is obtained. The polymeric nature of this material in solid state is confirmed through X-ray analyses (figure 1). It consists of polymeric chains formed by repetition of Au2Ag2 moieties linked through short gold-gold interactions. Nevertheless, in solution, the nature of this polymeric materials was still a matter of controversy and, in this case, the optical properties have been shown as useful tools in order to obtain information. Thus, while dilute acetone solutions of this complex give a emission coming from pentafluorphenyl localized ??* excited states, in accord with the presence of isolated tetranuclear Au2Ag2 units, when the measurements are done at different and higher concentrations, a band that does not obey the Lambert-Beer law appears. This deviation is consistent with molecular aggregation in solution of these units through gold-gold interactions, and a clear correlation between the emssion wavelength and the structure in the solid state and in solution is shown (figure 2). DFT calculations accord with the observed experimental behaviour and show the nature of the orbitals involved in each transition.