Synthèse et caractérisation de polymères semi-conducteurs à base de 5-alkyl [3,4-c] thienopyrrole-4,6-dione

Cette thèse porte sur la synthèse et la caractérisation de polymères à base de 5-alkyl[3,4-c]thienopyrrole-4,6-dione (TPD). Une importance particulière a été allouée aux aspects synthétiques entourant la conception de ces polymères. En premier lieu, nous avons étudié la réaction de polycondensation par hétéroarylation directe (DHAP) entre une unité TPD et une unité bithiophène. Le polymère obtenu par DHAP a été entièrement caractérisé et ses propriétés ont été comparées avec celles d’un polymère homologue fait par couplage de Stille. En second lieu, nous avons élaboré une voie de synthèse menant à un intermédiaire clef : le TPD possédant un atome d’iode en position 2. Cet intermédiaire permet, de façon simple et peu coûteuse, la confection de nouveaux monomères et polymères. Finalement, en unifiant les concepts développés au cours de nos travaux sur la DHAP et le TPD mono halogénés, nous avons simplifié davantage la synthèse de certains monomères et polymères de TPD. Nous avons également conçu une nouvelle série d’homopolymères et de pseudohomopolymères de TPD. Ces matériaux ont été caractérisés et des corrélations ont été faites entre les structures et les propriétés de ces polymères.This thesis is devoted to the synthesis and characterization of 5-alkyl[3,4-c]thienopyrrole-4,6-dione (TPD) based polymers. The focus of our work is the synthetic aspects surrounding the design of these polymers. First, we studied the direct heteroarylation polycondensation reaction (DHAP) between TPD and bithiophene monomers. The polymer obtained by DHAP was fully characterized and its properties were compared with those of a homologous polymer made by Stille coupling. Secondly, we developed a synthetic route leading to a key intermediate, which is the TPD molecule functionalized with one iodide. This intermediate can be used to synthesize new monomers and polymers in a simple and inexpensive way. Finally, by merging the concepts developed during our work on the DHAP and mono halogenated TPD, we further simplified the synthesis of certain TPD based monomers and polymers. We also designed new series of homopolymers and pseudohomopolymers TPD. These polymers have been characterized with correlation between structures and properties have been evaluated

[(IMes)2Pt(H)(ClBC5H4SiMe3)] : a Borabenzene–Platinum Adduct with an Unusual Pt‐Cl‐B Interaction

A Pt‐Cl‐B interaction is observed when a borabenzene derivative reacts with a platinum(0) precursor with bulky N‐heterocyclic carbene ligands. The resulting platinum(II) complex (see picture; Pt red, N blue, Cl green, B pink, Si yellow) involves a new bonding mode for borabenzene, which usually binds in an η6 fashion to transition metals

Roadmap on Photovoltaic Absorber Materials for Sustainable Energy Conversion

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.Comment: 160 pages, 21 figure

Low-Cost Synthesis and Physical Characterization of Thieno[3,4‑<i>c</i>]pyrrole-4,6-dione-Based Polymers

The improved synthesis of thieno­[3,4-<i>c</i>]­pyrrole-4,6-dione (TPD) monomers, including Gewald thiophene ring formation, a Sandmeyer-type reaction, and neat condensation with an amine, is presented. This protocol enables faster, cheaper, and more efficient preparation of TPD units in comparison to traditional methods. Furthermore, a series of TPD homo- and pseudohomopolymers bearing various alkyl chains was synthesized via a direct heteroarylation polymerization (DHAP) procedure. UV–visible absorption and powder X-ray diffraction measurements revealed the relationship between the ratio of branched to linear alkyl chains and the optoelectronic properties of the polymers as well as their packing in the solid state

A Thieno[3,4-c]pyrrole-4,6-dione-based copolymer for efficient solar cells

Peer reviewed: YesNRC publication: Ye

High Open-Circuit Voltage Solar Cells Based on New Thieno[3,4-<i>c</i>]pyrrole-4,6-dione and 2,7-Carbazole Copolymers

New alternating copolymers derived from thieno­[3,4-<i>c</i>]­pyrrole-4,6-dione (TPD) and 2,7-carbazole moieties have been synthesized by Suzuki cross-coupling reaction and characterized. These polymers combine interesting properties such as good solubility and excellent thermal and air stability. The present studies indicate that the combination of TPD and 2,7-carbazole building blocks can be a very effective way to lower the HOMO energy level and ultimately to enhance the <i>V</i>_oc of polymer solar cells. The <i>V</i>_oc reported here (up to 1.07 V) is one of the highest observed for polymer:[60]­PCBM bulk heterojunction devices, and preliminary results on the photovoltaic devices (power conversion efficiencies up to 1.8%) indicate that performance could probably be improved by increasing the molecular weights and by fine-tuning the electronic properties and the morphology