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Séminaire Chimie ED459

Promoting CO2 as a tecton in supramolecular science and urban mining

Dr. Julien Leclaire (Équipe CSAp Chimie Supramoléculaire Appliquée, ICBMS Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 CNRS, Université Lyon 1)

publié le

Le Jeudi 02 Octobre 2014 à 13h45
UM2, salle de cours SC-12.01

From trivial polyamines and polyaldehyde building blocks, a dynamic combinatorial selection approach can quantitatively yield an architecturally complex organic material, in which carbon dioxide is reversibly but covalently incorporated as a guest with a mass content of 20%. State of the art correlations between experimental and computed X-ray powder and solid state NMR spectra provide a clear picture of the three-dimensional organization of the assembled oligomeric adducts. The thermodynamic selection process appears to be directed by the stereoregular packing efficiency of the selected macromolecules, underpinning the spectacular building block discrimination observed between close homologues, including chiral polyamines from achiral ones. Under the sorting pressure of CO2, the self-assembly of the constitutive oligomers occurs through the simultaneous creation of more than 25 covalent bonds per molecular entity. A simple hydrolytic disconnection can provide the pure molecular building blocks selected during the self-assembling process from mixtures of high degree of diversity, as a result of the combined constitutional selectivity and the reversibility of the system.

This phenomenon paves the way toward the use of CO2 as a green auxiliary to purify organic and inorganic building blocks from complex mixtures of homologues. As the connecting pattern (imine and carbamate) are notorious ligating units for metals, such multi-component networks based on CO2 could be successfully used to sequester strategic metals with unprecedented selectivity. As pressure or temperature can act as physical stimuli to selectively expel the gas template from these multi-component self-assembled solids, yielding back the initial libraries, this dynamic combinatorial approach can be envisaged for the design of green processes of urban mining from technological waste. These results underline the potential contribution of System Chemistry to carbon dioxide sequestration and metal recycling. Reversibly, it also brings the proof that CO2 can indeed act as a molecular tecton in System Chemistry by driving sorting processes and yielding complex and polyfunctional assemblies.

Figure 1. Self-assembling of CO2-based multi-component supramolecular material

Figure 1 (cliquer pour agrandir)

References

a. J. Leclaire, G. Husson, N. Devaux, V. Delorme, L. Charles, F. Ziarelli, P. Desbois, A. Chaumonnot, M. Jacquin, F. Fotiadu, G. Buono. J. Am. Chem. Soc. 2010, 132, 3582-93 ;
b. F. Fotiadu, M. Jacquin, J. Leclaire, A. Methivier. French Patent 2012 FR2969503 ;
c. F. Fotiadu, M. Jacquin, J. Leclaire, A. Methivier. French Patent 2102 FR2969504 ;
d. G. Poisson, J. Leclaire, F. Fotiadu, G. Canard. French Patent PCT/FR2013/054510 ;
e. G. Poisson, J. Leclaire, F. Fotiadu, G. Canard, French Patent PCT/FR2014/051172

Contacl local IBMM : Dr. Laurent Vial (équipe DSBC)

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