Frustrated Lewis Pairs Catalysts inside Molecularly Defined Porous Solid Matrix – FLIPS

The direct transformation of small organic molecules or even CO2 into valuable synthetic intermediates is of key importance to increase the sustainability of chemical industry. There is an ever-growing need to develop novel catalytic systems based on earth-abundant low cost elements with a broad-span capability for providing value-added compounds for the sustainable production of chemicals.

To change the paradigm of catalytic processes for fine chemicals production, FLiPS will develop the heterogenization of molecular frustrated Lewis Pairs (FLPs) inside the porous cavity of hybrid materials in order to generate a new family of heterogeneous single-site catalysts for the synthesis of value-added chemicals from small molecules. FLiPS strategy will allow recyclability and easy separation while maintaining both the molecular nature of the active site and its high activity. Two complementary types of microporous materials, i.e. metal-organic frameworks (MOF) and porous organic polymers (POP) will be used as organo-based matrix for the heterogenization of FLPs. The hosting micropores will ensure FLP’s molecular integrity by immobilization in a robust structure.

The objective of FLiPS is to demonstrate that the covalent functionalization of well-selected porous solids with rationally designed FLPs will provide novel heterogeneous FLP@MOF or FLP@POP catalysts, exhibiting great potential for developing a novel chemistry for the activation of small inert molecules and highly selective reactions. This will be exemplified in the proof-of-concept hydrogenation of CO2 into value-added chemicals like formic acid and methanol, as well as in the C=O and C=N bonds hydrogenation for fine chemicals synthesis.

FLiPS gathers efforts in molecular chemistry, material science, computational chemistry and catalysis. In an highly integrated approach, catalysts synthesis and computational chemistry are conducted in parallel to accelerate the finding of efficient systems.The synthesis of FLP-functionalized porous solids is based on a rational approach driven by both state-of-the-art active molecular pairs and computational chemistry knowledge generated in FLiPS. Quantum mechanical calculations based on Density Functional Theory (DFT) level calculations coupled with Molecular Dynamics (MD) allow getting a set of reachable FLP structures and the corresponding transition states for the targeted reactions.Advanced Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy technique (DNP SENS) as well as infrared spectroscopy using synchrotron irradiations are used in conjunction with DFT calculations and provide further atomic level insights. Amongst others, FLP@solid catalysts are evaluated in the carbon dioxide hydrogenation, chosen as proof-of-concept reaction.

Overall, the ground-breaking nature of FLiPS lies in earth-abundant heterogeneous catalysts offering an unprecedented sustainability to reduction processes compared to the state-of-the-art. FLiPS will bring novel effective methods to manipulate solid surfaces aiming at building fully heterogeneous FLP. FLiPS multidisciplinary approach, based on computational chemistry tightened to experiments on the heterogenization of site-isolated molecular FLP inside molecularly defined porous structure, has never been explored so far and brings key concepts together within a single material to achieve exceptionally high productivity and sustainability in catalytic reduction processes. The knowledge gained from FLiPS project about confinement and conformation of molecular active sites inside porous systems will never be available in homogeneous systems.