Synthesis of Metal Organic Thiolate Coordination

**Synthesis of Metal Organic Thiolate Coordination Polymers as Innovative Thermoelectric Materials**:

- Réf **ABG-126159**
- Stage master 2 / Ingénieur- Durée 6 mois- Salaire net mensuel 550 euros- 07/10/2024- Institut de Recherches sur la Catalyse et l'Environnement de Lyon- Lieu de travail- Villeurbanne Auvergne-Rhône-Alpes France- Champs scientifiques- Chimie
- Matériaux
- Mots clés- Coordination polymers, solid state chemistry, conductivity-
- 29/11/2024**Établissement recruteur**:
**Site web**:
Among the characterization methods available are: single crystal and powder X-Ray diffraction; IR, Raman, UV-vis and XPS spectroscopies; N2 adsorption, SEM and TEM, TGA-DTA and DSC.

Internship will take place in collaboration with Dr Gilles Ledoux (emission, excitation and lifetime measurements), and Dr Stéphane Pailhes (conductivity measurements, shaping techniques) in ILM on the Doua campus.

**Description**:

- Aside from our reliance on fossil fuel, one of the challenges of the energy use in our modern society is the huge untapped amount of waste heat generated, which cannot be harnessed and utilized with today thermoelectric (TE) materials. Indeed, all the industrial machineries, the combustion engines and batteries in automobiles, the thermal and nuclear power plants and most technological equipment produce heat, even our human bodies, which when being left untapped, is forever lost, counting almost 70 % of the total energy used today.1 Therefore, to move forward and to tap this mostly unused resource, **new and efficient thermoelectric materials should be developed to convert waste heat into green and renewable electricity**. Solving this challenging problem would provide a new pathway to green energy revolution and the discovery of advanced TE materials would change our energy system and make significant contributions to lessen the reliance on fossil fuels.- The power conversion efficiency of a TE material scales with a dimensionless figure of merit _ZT_ = (σS2T) / k, where σ is the electrical conductivity, S the Seebeck coefficient, k the thermal conductivity, and T the absolute temperature. Although major breakthroughs have been done at the beginning of the century, all the commercially available TE generators suffer from their very low conversion efficiencies, which are due to their limited _ZT_. Research efforts have been mostly focused in semi-conducting inorganic materials bringing on stage efficient materials like Bi2Te3, SiGe, skutterudites...Thus, to improve this _ZT_, novel TE materials have to be developed. Since _ZT_ is inversely proportional to the thermal conductivity, it is required to have TE materials with very low thermal conductivity, close to zero, and high electrical conductivity. **Coordination polymers (CPs) have recently appeared as a good alternative to inorganic TE materials**.2 Indeed, their composition of metals, organic ligands and coordinating functional groups can lead to an infinite of materials with 1D, 2D, or 3D structured materials. Recent progresses show that sulfur-based CPs exhibit the best electrical conductivity compared to oxygen one.3 Thus, with anisotropic CPs, it is possible to build metallic layers or chains efficient for charge transport, while the organic surroundings will act as a heat insulator.

The goal of the internship, based on the expertise of A. Demessence team on thiolate-based CPs,4 is to synthesize new **conducting** **thiolate-based CPs with original thiol molecules for a complete structure/electronic properties understanding**. During this internship project, it is proposed to work with series of compounds based on multidentate thiol-based ligands associated to different functions (-NH2, -CO2H, -OH, -F) and copper and silver metals, in order to obtain different network dimensionalities and n
- 1 D. M. Rowe, _Thermoelectrics Handbook: Macro to Nano_, (Taylor & Francis Ltd., 2006).- 2 E. Redel; H. Baumgart, _APL Mater._, 2020, **8**, 060902.- 3 Y. Kamakura; D. Tanaka, _Chem. Lett._, 2021, **50**, 523.- 4 (a) O. Veselska; A. Demessence, _Coord. Chem. Rev._, 2018, **355**, 240; (b) S. Vaidya; O. Veselska; A. Zhadan; M. Diaz-Lopez; Y. Joly; P. Bordet; N. Guillou; C. Dujardin; G. Ledoux; F. Toche; R. Chiriac; A. Fateeva; S. Horike; A. Demessence, _Chem. Sci._, 2020, **11**, 6815; (c) O. Veselska; N. Guillou; M. Diaz‐Lopez; P. Bordet; G. Ledoux; S. Lebègue; A. Mesbah; A. Fateeva; A. Demessence, _ChemPhotoChem_, 2022, **6**, e202200030; (d) O. Veselska; S. Vaidya; C. Das; N. Guillou; P. Bordet; A. Fateeva; F. Toche; R. Chiriac; G. Ledoux; S. Wuttke; S. Horike; A. Demessence, _Angew. Chem. Int. Ed._, 2022, **61**, e202117261; (e) A. Abdallah; S. Vaidya; S. Hawila; S.L. Ornis; G. Nebois; A. Barnet; N. Guillou; A. Fateeva; A. Mesbah; G. Ledoux; A. Bérut; L. Vanel; A. Demessence, _iScience_, 2023, **26**, 106016; (f) C. Andrade; S. Hawila; A. Abdallah; J.L. Rukemampunzi; A. Mesbah; N. Guillou; F. Perret; S. Wuttke; T. Niehaus; R. Debord; O.