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Poster De Conférence Année : 2017

Structural and photophysical studies of Au(I)-thiolate coordination polymers

O. Veselska
  • Fonction : Orateur
  • PersonId : 1005446
N. Guillou
  • Fonction : Auteur
G. Ledoux
D. Podbevsek
  • Fonction : Auteur
A. Fateeva
A. Demessence
  • Fonction : Auteur

Résumé

Hybrid 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 interactions implying luminescence.[1] Among them, gold(I) thiolates are an important class of materials, that can generate oligomeric or polymeric structures due to the high affinity of gold for sulfur atoms. This also implies a high reactivity between thiols gold precursor and the formation of insoluble products. Thus, a little is known about their structure and the origin of the photophysical properties. Only three crystallographic structures of gold(I) thiolates coordination polymers have been reported: two having double interpenetrated helical chains[2] and one having a lamellar structure.[3] Among them two exhibit red photo-emission with extreme quantum yields of around 5 and 70 % in solid state at room temperature. Thus, a little is known about the origin of the photoluminescence of gold thiolate coordination polymers and the relation with the structure and the effect of the ligands. Here we present syntheses and structure resolutions by powder X-Ray diffraction of three new Au(I)-thiophenolate-based lamellar compounds: [Au(oSPhNH2)]n, [Au(pSPhCOOH)]n and [Au(mSPhCOOH)]n. The first one, amino function, forms double interpenetrated helical chains, as already reported [Au(SPh)]n,[2] but is emissive in the near infra-red. The two other compounds with carboxylic acids in para and meta position have lamellar structures with a quite similar helical and parallel Au(I)-S chains (Fig. 1). Nevertheless, aurophilic distances between the chains are a bit different. Thus, despite the structures are quite similar, the photophysical properties are different. [Au(mSPhCOOH)]n exhibits only one emission peak centered at 600 nm that originates from Ligand-to-Metal-to-Ligand Charge Transfer, meanwhile [Au(pSPhCOOH)]n shows dual emission with peaks at 495 and 650nm that originate from Ligand Charge Transfer and Ligand-to-Metal-to-Metal Charge Transfer respectively. The study shows for the first time the sensitivity and richness of structures and photophysical properties of gold thiolate coordination polymers. With this high tunability we valorize these materials as either lighting applications or as an optical thermometer with the thermochromic solid. References 1. H. Schmidbaur, A. Schier, Chem. Soc. Rev., 2012, 41, 370-412. 2. C. Lavenn, L. Okhrimenko, N. Guillou, M. Monge, G. Ledoux, C. Dujardin, R. Chiriac, A. Fateeva, A. Demessence, J. Mater. Chem. C, 2015, 3, 4115-4125. 3. C. Lavenn, N. Guillou, M. Monge, D. Podbevšek, G. Ledoux, A. Fateeva, A. Demessence, Chem. Commun., 2016, 52, 9063-9066.
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Dates et versions

hal-01541407 , version 1 (19-06-2017)

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  • HAL Id : hal-01541407 , version 1

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O. Veselska, N. Guillou, G. Ledoux, D. Podbevsek, A. Fateeva, et al.. Structural and photophysical studies of Au(I)-thiolate coordination polymers. Journée de Printemps de la SCF-RA, Jun 2017, Chambéry, France. ⟨hal-01541407⟩
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