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2021年秋季法國(guó)巴黎大學(xué)分子電化學(xué)實(shí)驗(yàn)室Claire Fave教授誠(chéng)招CSC公派博士生
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Title: Novel electrocatalytic processes with molecular catalysts involving non-covalent interactions. Advisors: Dr. C. Fave, Dr. A. Guerlin and Pr. B. Schöllhorn Mail: claire.fave@u-paris.fr Lab: Laboratoire d’Electrochimie Moléculaire (LEM) UMR 7591, Université de Paris, Bat . Lavoisier, 15 rue J.-A. de Baïf, 75205 Paris Cedex 13, France Sector : Science Funding type: 48 months Description of the subject Inter- and intramolecular non-covalent interactions play a fundamental role in synthesis, catalysis, crystal engineering, electrochemistry, molecular recognition, biology, material sciences. Interactions, such as hydrogen, halogen, chalcogen bonds, but also cation/anion–π, π–π stacking impact energetics and structures of molecular catalysts and consequently their reactivity in terms of reaction kinetics and selectivity.[1,2] In fact, non-covalent interactions play an essential role in the action of Nature's catalysts, enzymes, by decreasing energy barriers of reaction through transition-state stabilization. The precise bonding parameters (strength, directionality, etc.) of such interactions are difficult to determine even though they are crucial for the control of stereo- or regioselectivity. The selectivity of catalytic reactions is often an orchestrated action of various non-covalent interactions occurring prior to or in the transition state. An in-depth understanding of these weak forces can lead to the design of more efficient synthetic catalysts allowing for a better reactivity control. In the emerging field of organocatalysis, hydrogen bonding (HB) is one of the most frequently used interactions. However, inspired by the success of HB in this field, chemists are particularly interested to explore the use of other weak interactions. [3] Based on the knowledge and concepts developed in our team combining electrochemical detection and control of weak interactions in solution and at the electrode interface,[4] we are now investigating redox-catalytic processes based on molecular catalysts involving non-covalent interactions. For this purpose, the synthesis of new metallic complexes will be performed and their electrochemical and catalytic properties will be systematically studied by spectroscopic, electrochemical and spectro-electrochemical methods. This challenging and innovative topic is situated at the still underexplored frontiers between catalysis, supramolecular chemistry and electrochemistry. Expected skill of the PhD candidate: organic chemistry, metal complexes synthesis, molecular electrochemistry. [1] Noncovalent Interactions in the Synthesis and Design of New Compounds, ed. A. M. Maharramov, K. T. Mahmudov, M. N. Kopylovich and A. J. L.Pombeiro, John Wiley & Sons, Inc., Hoboken, NJ, 2016 [2] Noncovalent Interactions in Catalysis, ed K. T. Mahmudov, M. N. Kopylovich, M. F. C. Guedes da Silva, A. J. L. Pombeiro, Royal Society of Chemistry, 2019. [3] R. L. Sutar, S. M. Huber, ACS Catal, 2019, 9, 9622-9639. [4] a) Fave, C.; Schöllhorn, B. Current Opinion in Electrochemistry, 2019, 15, 89-96; b) Hijazi, H.; Vacher, A.; Groni, S.; Lorcy, D.; Levillain, E.; Schöllhorn, B.; Fave, C. Chem. Comm. 2019, 55, 1983-1986; c) Groni, S.; Maby-Raud, T.; Fave, C.; Branca, M.; Schöllhorn, B. Chem. Commun. 2014, 50 (93), 14616-14619. |
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