Switchable molecular cages as catalysts Laboratoire de Synthèse des Assemblages Moléculaires Multifonctionnels (LSAMM), Institut de Chimie UMR7177, Université de Strasbourg. Project Molecular cages with a three dimensional active cavity able to bind reversibly guest molecules are highly attractive for sensor or transport applications, for drug delivery or to perform a chemical reaction in a confined environment.[1] Porphyrins as constituents of a cage framework offer several ways to be active partners in the cage activity due to their coordination, redox, electronic and photophysical properties.[2] Controlling the release of a guest from a molecular container or of a product formed within a nanoreactor is particularly important for controlled guest delivery or catalysis. One way to obtain such function is to trigger a large conformational change of the structure to modify the size of the cavity. Such an approach has not yet received much attention, despite the scientific challenge of building enzyme-like machinery. The aim of this project is to synthesize dynamic cages incorporating peripheral regulation sites to trigger, under the action of an external stimulus, a modulation of the cavity size in order to perform controlled guest delivery and switchable catalysis. The flexible covalent cages will incorporate orthogonal coordination and regulation sites: metalloporphyrins for substrate binding within the cavity and ligands on the periphery to modulate the cage activity.[3] The cavity of the flexible cages will shrink or expand in response to different chemical stimuli interacting with the peripheral ligands. These unique systems have indeed an appealing potential as on/off switchable catalysts that will be exploited. One reaction of interest is the catalytic carbon dioxide activation. We will test our systems as molecular catalysts to obtain carbonates or polycarbonates. [1]. a) T. S. Koblenz, J. Wassenaar, J. N. H. Reek, Chem. Soc. Rev. 2008, 37, 247-262; b) M. D. Pluth, R. G. Bergman, K. N. Raymond, Acc. Chem. Res. 2009, 42, 1650-1659; c) J. Rebek, Acc. Chem. Res. 2009, 42, 1660-1668; d) M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed. 2009, 48, 3418-3438; e) R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem. Rev. 2011, 111, 6810-6918; f) M. J. Wiester, P. A. Ulmann, C. A. Mirkin, Angew. Chem. Int. Ed. 2011, 50, 114-137; g) M. M. J. Smulders, I. A. Riddell, C. Browne, J. R. Nitschke, Chem. Soc. Rev. 2013, 42, 1728-1754. [2]. S. Durot, J. Taesch, V. Heitz, Chem. Rev. 2014, 114, 8542-8578. [3]. a) J. Taesch, V. Heitz, F. Topic, K. Rissanen, Chem. Commun. 2012, 48, 5118-5120; b) S. Durot, L. Flamigni, J. Taesch, T. T. Dang, V. Heitz, B. Ventura, Chem. – Eur. J. 2014, 20, 9979-9990. ____________________________________________________________________________ : + 33 (0)368851359 : + 33 (0)368851357 : [email protected] : [email protected] http://www.lsamm.fr/ : Laboratoire Synthèse des Assemblages Multifonctionnels - Institut de Chimie Bâtiment Le Bel, 5ème étage Nord, 4, Rue Blaise Pascal – CS 90032 - F-67081 Strasbourg Cedex France Position: post-doctoral for one year, starting from September 2015. Financial support: ANR JCJC Net salary: 2120 €/month Candidate: the candidate should have a high quality PhD degree in chemistry, high skills and affinity with organic synthesis, coordination chemistry and supramolecular chemistry. Experience in homogeneous catalysis would be greatly appreciated. In terms of personal skills, perseverance, creativity, enthusiasm and a good team spirit are essential. Strong motivation for research in a competitive domain is expected. English fluency is highly desired. Application: send a detailed CV with the contact address of two referees and one recommendation letter to Dr. Stéphanie Durot ([email protected]) and Prof. Valérie Heitz ([email protected]) ____________________________________________________________________________ : + 33 (0)368851359 : + 33 (0)368851357 : [email protected] : [email protected] http://www.lsamm.fr/ : Laboratoire Synthèse des Assemblages Multifonctionnels - Institut de Chimie Bâtiment Le Bel, 5ème étage Nord, 4, Rue Blaise Pascal – CS 90032 - F-67081 Strasbourg Cedex France
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