Luminescent Gold(I)-Thiophenolate Coordination Polymers as Phase Change Materials and Precursors for theFormation of Multifunctional Nanocomposites

SSCI-VIDE+CDFA+ADM:OVEInternational audienceHybrid Au(I) compounds exhibit a large domain of applications such as electronic devices, contrast agents,sensors or photocatalysts. These applications are related to the ability of gold(I) to form aurophilic interactionsimplying self-assembly and luminescence.1 Among them, gold(I) thiolates are an important class of materials due tothe high affinity of gold for sulfur atoms that can generate oligomers or polymers. However due to the fast precipitationand the insolubility of these solids, a little is known about their structure and the origin of the photoluminescence. Wepresent the syntheses and the first structure resolutions, by powder X-Ray diffraction, of series of gold(I)-thiophenolate-based compounds. Depending on the substituent different structures are obtained: lamellar, helicoidalor cyclic (Fig. 1a). The photophysical properties of these hybrid materials are studied in solid-state and coupled withDFT calculations. These analyses show that the charge transfer from Ligand-to-Metal or Metal-to-Ligand and thequantum yield from few percentage to 70%, can be tuned with the electrophilicity of the thiolates.2-3 Among thosecoordination polymers, two exhibit dynamic OFF/ON emission switching, one associated with a thermally inducedsolid-state phase change from amorphous to crystalline2 and the other one from a reversibleesterification/saponification. Finally we synthesized luminescent, crystalline and flexible fibers of [Au(SPh)]n andgenerated by calcination composite materials mixing gold nanoparticles (GNP) and fibers (Fig. 1b and c). This studyshows the great potential of gold thiolates as phosphorescent hybrid materials and as precursors for the formation ofmultifunctional nanocomposites coupling plasmonic and luminescence in electronic devices or photocatalysis.1. H. Schmidbaur, A. Schier, Chem. Soc. Rev., 41, 370, 2012.2. C. Lavenn, L. Okhrimenko, N. Guillou, M. Monge, G. Ledoux, C. Dujardin, R. Chiriac, A. Fateeva, A. Demessence,J. Mater. Chem. C, 3, 4115, 2015.3. C. Lavenn, N. Guillou, M. Monge, D. Podbevšek, G. Ledoux, A. Fateeva, A. Demessence, Chem. Commun., 52,9063, 2016