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. 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. 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. 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.
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Publications of LSAMM laboratory researchers in these fields of research.
" Design and synthesis of porphyrin-containing catenanes and rotaxanes ".LINK
J.A. Faiz, V. Heitz, J.-P. Sauvage, Chem. Soc. Rev., 2009, 38, 422.
Highlight: Chemical Science 2009, 6, C1-C8.
" An adjustable receptor based on a rotaxane whose two threaded rings are rigidly attached to two porphyrinic plates : synthesis and complexation studies ".LINK
J.-P. Collin, J. Frey, V. Heitz, J.-P. Sauvage, C. Tock, L. Allouche, J. Am. Chem. Soc., 2009, 131, 5609.
" Quantitative formation of a tetraporphyrin catenane via copper and zinc coordination ".LINK
M. Beyler, V. Heitz, J.-P. Sauvage, Chem. Commun., 2008, 5396.
" A ruthenium-based metalostar: synthesis, sensitized luminescence and 1H relaxivity ".
L. Moriggi, A. Aebischer, C. Cannizzo, A. Sour, A. Borel, J.-C. Bünzli, L. Helm, Dalton Trans., 2009, 12, 2088.
" A starburst-shaped heterometallic compound incorporating six densely packed Gd3+ ions". LINK
Livramento, J.B.; Sour, A.; Borel, A.; Merbach, A.E.; Toth, E., Chem. Euro. J., 2006, 12, 989.
" Azide chemistry in rotaxane and catenane synthesis",
in Organic Azides:
Syntheses and applications, Wiley, S. Bräse, K. Banert Eds, Durot, S., Frey, J., Sauvage, J.-P., Tock, C. in press.
" Series of Mn complexes based on N-centered ligands and superoxide–reactivity in an anhydrous medium and SOD-like activity in an aqueous medium correlated to MnII/MnIII redox potentials". Durot, S., Policar, C., Cisnetti, F., Lambert, F., Renault, J.-P., Pelosi, G., Blain, G., Korri-Youssouffi, H., Mahy, J.-P, Eur. J. Inorg. Chem., 2005, 17, 3513.
Laboratory : Synthèse des Assemblages Moléculaires Multifonctionnels