CE06 - Polymères, composites, physique et chimie de la matière molle, procédés

Self-Assembled Metal-Acetylides for Thermoelectrics – SAMAT

Submission summary

Thermoelectrics (TE) stands out as a concrete alternative way for green energy production. Thermoelectric material converts waste heat into electricity, thanks to high charge transport and low heat transport between two electrodes. Up to now, TE materials relied on the well-investigated high mobility organic semiconductors, such as conjugated polymers and to smaller extent 2D self-assembled small molecules. Although impressive progresses were documented, we are still far away from a concrete technological development. Organic TE dramatically suffers from a poorly investigated organic semiconductors structure-property relationships, from limited material category range, unclear working mechanisms and finally, the lack of an empirical methodology that would allow genuine, rational comparisons between TE materials.

SAMAT aims at i) developing unique nanostructured materials comprising 1D self-assemblies of organometallic small molecules fibers or ribbons, by means of solvent gelation, ii) investigating their supramolecular characteristics and iii) studying their electrical/thermal/Seebeck properties in TE devices. The small molecules under investigation are metal bis-acetylides, mono-and bimetallic organometallic complexes where the metal is FeII, RuII or OsII.
Supramolecular materials comprising entangled 1D supramolecular fibers or ribbons represent a chance to find the proper combination of important electrical conductivity (high molecular ordering due to self-assembled molecules) and low thermal conductance (supramolecular nature of the 1D objects). By virtue of judicious comparisons between the supramolecular materials, we wish to extract fundamental structure-property relationships.

The SAMAT project is divided in three tasks.
-Task 1. The main goal is to establish a comprehensive methodology for efficient 1D self-assemblies of RuII bis-acetylides. To do so, model symmetric monometallic Ru-complexes containing 1,2-dppe (1,2-Bis(diphenylphosphino)ethane) bidentate ligands will be first investigated. Based on our preliminary work (vide infra) and by a rationalized molecular engineering, we wish to control the self-assembly properties of these objects, resulting in a molecular structure - supramolecular properties relationship. Eventually, these supramolecular architectures will be characterized by means of their morphological, electronic, gelation efficiencies and finally by TE measurements (impact of 1D nanostructuration on TE performances).
-Task 2 will prolong the achievements of Task 1 by building comprehensive model of self-assembly for a class of bimetallic complexes comprising the same (1,2-dppe) RuII bis-acetylides building block. These complexes should offer lower oxidation potentials and therefore the corresponding materials should present higher electrical conductivity. As in Task 1, the supramolecular assemblies will be studied in detail in terms of morphology, packing etc… The TE performances will be recorded and the impact of the material's nanostructuration will be investigated.
-Task 3 will extend the principles developed in Task 1&2 to other metals such as Fe and Os. By comparing materials with identical 1D supramolecular objects, we will extract useful information about the mechanistic aspects of the Seebeck effect and draw important correlation. In addition, it will be the opportunity to study the influence of the metal on the TE performances.

Project coordination

Olivier Galangau (INSTITUT DES SCIENCES CHIMIQUES DE RENNES)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

INRS / Physique moléculaire et du dispositif
ISCR INSTITUT DES SCIENCES CHIMIQUES DE RENNES

Help of the ANR 223,851 euros
Beginning and duration of the scientific project: - 48 Months

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