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法国巴黎萨克雷大学（Université Paris-Saclay）课题组招收2021年CSC博士
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课题组介绍：http://www.ilv.uvsq.fr/en 项目介绍：csc项目 招生类型： 1. 应届与往届硕士毕业生 招生要求： 1. 性格开朗，勤奋好学； 2. 具有很强的有机合成功底; 3. 有至少一篇一作的英文文章; 4. 需要与课题组一起申请csc。 课题1: Synthesis and characterisation of new Kekuléan biradicaloid systems and centred carbon- and aromatic nitroxide-free radicals This project is a continuation of the work recently undertaken on -conjugated systems (1,2) and in particular on so-called Kekuléan biradicaloid systems. These molecules are resonance hybrids between a Kekulé form (closed shell) where all electrons are paired and a biradical form with two unpaired electrons (open shell). The driving force to be biradical in the ground state is related to the aromatic stabilization of the biradical form. So far, Kekuléan biradicaloid systems have Kekulé forms which are either molecules with low aromaticity or quinoidal molecules which are non-aromatic. The project proposes to synthesize Kekuléan biradicaloid molecules for which the Kekulé form will be strongly antiaromatic with 4n-electrons at the centre of the molecules. Given the strong antiaromaticity, the molecules will prefer to open up to generate aromatic subunits in the biradical forms which will be the predominant forms in the ground state. The biradical character of the molecules will be very high and the molecules could be considered as nearly pure biradical form with low singlet-triplet energy gap. In order to obtain stable molecules, the design among others is based on the "syn-annelation" for the external cycles which has proved its efficiency both for the free radical based on dibenzofluorene and for Kekulé biradicaloid systems. Another field that will be undertaken, is related to the preparation of stable centred carbon free radicals5 and aromatic nitroxide radicals6 that could be the next generation of materials for flexible electronics. Reference : 1. M. Frigoli et al., Chem. Sci., 2020, 11, 12194. « Modulating the ground state, stability and charge transport in OFETs of biradicaloid Hexahydro-diindenopyrene derivatives and a proposed method to estimate the biradical character ». 2. M. Frigoli et al., J. Am. Chem. Soc., 2019, 141, 9373. « Excellent semiconductors based on tetracenotetracene and pentacenopentacene: from stable closed-Shell to singlet open-Shell ». 联系人: Michel Frigoli (michel.frigoli@uvsq.fr) and Karen Wright (karen.Wright@uvsq.fr), University Paris-Saclay, Institut Lavoisier de Versailles 课题2: Synthesis and characterisation of organic semiconductors for OFET and OLET applications The project will be dedicated to the synthesis of organic semiconductors for OFET and OLET applications. While many organic semiconductors have been prepared for the above applications, there are still some rooms for high improvements.(3-5) Reference : 3. Y. Geerts et al., Adv. Mater,. 2020, 32, 1905909. « Molecular semiconductors for logic operations: Dead-end or bright future? ». 4. J. Takeya et al., J. Am. Chem. Soc., 2020, 142, 9083. « Bent-shaped p‐type small-molecule organic semiconductors: A molecular design strategy for next-generation practical applications ». 5. H. Fuchs et al., Nat Commun., 2019, 10, 12. « Band-like transport in small-molecule thin films toward high mobility and ultrahigh detectivity phototransistor arrays ». The candidate should have a good communication skill in English both writing and speaking (French is not mandatory) and have a strong background in organic synthesis and willing to work at the interface Chemistry/Physics. The PhD student will be focused on the synthesis of the target molecules and basic characterisations such RMN, mass, infrared and UV/vis spectroscopies and electrochemistry, EPR and X- ray diffraction. The work will be done at the University Paris-Saclay at the Lavoisier Institute located at Versailles City. In the course of the PhD thesis, a trip to Adachi’s group (Japan) can be planned for the advanced characterisation of the materials. 联系人: Michel Frigoli (michel.frigoli@uvsq.fr) and Karen Wright (karen.Wright@uvsq.fr), University Paris-Saclay, Institut Lavoisier de Versailles 课题3: Cooperative combination of weak interactions : application to molecular recognition and catalysis. The project focuses on the development of a new family of modular ligands for both molecular recognition and homogeneous catalysis. The design of the ligands is based on a combination of fragments able to generate different weak interactions within the same recognition/catalytic platform. Context : Anions play a central role in many biological and environmental processes but also more recently to catalysis. This statement has stimulated a lasting interest of the scientific community which rivals creativity to design efficient and selective receptors or ligands. The development of selective anion molecular receptors is thus a challenge mainly due to (i) the diversity of anion geometries e.g. spherical, linear, polyhedral (ii) the fact that only weak interactions and/or reversible weak interactions take place in dynamic processes. Efficiency of recepor is based on its capacity to generate weak non-covalent interactions such as hydrogen bonds, halogen bonds but also -anion bonds. Therefore, the design of these anion ligands / receptors is a challenge and has to by anticipated in order to target an ideal spatial arrangment for a selected combination of ligand/anion couple. These weak interactions individually contribute to the 3D shape and properties of complex molecular arcitectures, but their association within the same polyfunctional molecular platform will allow (i) combining several weak interactions (ii) likely modulating strength and selectivities (iii) fine tuning of properties or generating new properties. While hydrogen bonds remain a key interaction in elaborating anion complexes, this project targets the joint use of H-bonds and other weak interactions. In this contex, this project aims at desiging and further synthesizing a new familly of receptors/ligand. The complexation to mono- and poly-valent anions will be studied followed by the investigation of catalytic properties especially for Cl- anion complexes. References: 1. A.-S. Marques, et al. Org. Lett. 2018, 20, 792; 2. H. Boufroura, et al Chem. Eur. J. 2018, 24, 8656; 3. A.-S. Marques, et al. Angew. Chem. Int. Ed. 2019, 58, 9969; 4. R. Plais, et al ChemPhysChem 2020, 21, 1249. 联系人：http://www.ilv.uvsq.fr/synthese-organique-sorg Prof. Xavier MOREAU (xavier.moreau@uvsq.fr) and Prof. Damien PRIM (damien.prim@uvsq.fr) |
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