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The use of earth-abundant metals for the direct C-H activation through a heterogeneous protocol would allow reaching appealing sustainability for the synthesis and derivat-ization of fine chemicals since this approach would enable at the same time (i) the use of accessible resources, (ii) a beneficial atom- and step-economy of non-activated substrates, and (iii) the ability to reuse the catalyst and to easily separate it from products.1 To change the paradigm of molecular catalytic processes for fine chemical synthesis, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis.2 Here we show the heterogenization of an earth-abundant molecular nickel complex within the structure of a bipyridine bipyridine-based POP, namely BpyMP-1, used as a porous macroligand.3 To assess the actual coordination of the nickel to the bpy sites within the porous polymer and the molecular nature of the heterogenized Ni(bpy) catalyst, we correlate both typical ssNMR signals and IR bands of bipyridines to the nickel content determined by ICP-OES analysis. DFT calculations on molecular cluster models of the binding site futher confirm the dependence of this band intensity to the bipyridine nickelation. We then explored the catalytic potential of Ni@BpyMP-1 for the direct C-H arylation of benzothiophene in the presence of lithium bis(trimethylsilyl)amide (LiHMDS) in toluene. The 2-phenylbenzothiophene was obtained with 50% yield and 100% regioselectivity for the arylation of benzothiophene at the C2 position using 1wt%Ni@BpyMP-1 catalyst, determined to be the best from a series. The heterogenous Ni@BpyMP-1 was found to be applicable to other aryl electrophiles as well as other heteroarenes (Figure 1a). Further improvement was made through heterogenization of Ni catalyst within BpyMP-1 for free NH indole arylation with 41% yield in 3-phenyl-indole and 62% C3 selectivity over N-arylation when the Ni@BpyMP-1 catalyst was used compard to homogeneous reaction (Figure 1b).Then, we evaluated the ability of Ni@BpyMP-1 solids to be recycled in the C2 arylation of benzothiophene. The TON reaches approx. 44 per run using 1wt%Ni@BpyMP-1 in the presence of NaBH4 (Figure 1c). After seven consecutive catalytic runs, a cumulative TON of 316 was reached. This corresponds to a total productivity of 12 grams of 2-phenylbenzothiophene per gram of catalyst.Taking into account their robustness and their potential processability, the porous organic polymers used as macroligands for molecular catalysts further pave the way to molecularly defined and robust heterogeneous systems for a more sustainable synthesis of fine chemicals.This work has been carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996.References1.Mohr, Y. et al. Green Chem. 22, 3155–3161 (2020).2.Wisser, F. M. et al. Acs Catal. 8, 1653–1661 (2018).3.Mohr, Y. et al. ACS Catal. 11, 3507–3515 (2021).

The use of earth-abundant metals for the direct C-H activation through a heterogeneous protocol would allow reaching appealing sustainability for the synthesis and derivat-ization of fine chemicals since this approach would enable at the same time (i) the use of accessible resources, (ii) a beneficial atom- and step-economy of non-activated substrates, and (iii) the ability to reuse the catalyst and to easily separate it from products.1 To change the paradigm of molecular catalytic processes for fine chemical synthesis, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis.2 Having molecularly-defined active sites, porous macroligands have been found to drive the activity and the selectivity of heterogenized catalytic processes on a similar way as molecular ligands but with the advantage of the structuration in a three-dimensional framework3 and the confinement within a porous nanospace.4 Here we show the heterogenization of an earth-abundant molecular nickel complex within the structure of a bipyridine bipyridine-based POP, namely BpyMP-1, used as a porous macroligand.5 The molecularly-defined Ni@BpyMP-1 heterogeneous catalyst allows the C2-selective arylation of benzothiophene and thiophene and, to the best of our knowledge, the first heterogeneous C2-selective arylation of selenophene.First, to assess the actual coordination of the nickel to the bpy sites within the porous polymer and the molecular nature of the heterogenized Ni(bpy) catalyst, we correlate both typical ssNMR signals and IR bands of bipyridines to the nickel content determined by ICP-OES analysis. DFT calculations on molecular cluster models of the binding site futher confirm the dependence of this band intensity to the bipyridine nickelation. We then explored the catalytic potential of Ni@BpyMP-1 for the direct C-H arylation of benzothiophene in the presence of lithium bis(trimethylsilyl)amide (LiHMDS) in toluene. The 2-phenylbenzothiophene was obtained with 50% yield and 100% regioselectivity for the arylation of benzothiophene at the C2 position using 1wt%Ni@BpyMP-1 catalyst, determined to be the best from a series. The heterogenous Ni@BpyMP-1 was found to be applicable to other aryl electrophiles as well as other heteroarens. For thiophene and 2-methylthiophene, the corresponding arylation products could be isolated in average to good yields. More scarcely studied selenophene, an attractive motif for optoelectronics19 and bioactive compounds, could also be successfully arylated (Figure 1a). Further improvement was made through heterogenization of Ni catalyst within BpyMP-1 for free NH indole arylation with 41% yield in 3-phenyl-indole and 62% C3 selectivity over N-arylation when the Ni@BpyMP-1 catalyst was used compard to homogeneous reaction (Figure 1b).Then, we evaluated the ability of Ni@BpyMP-1 solids to be recycled in the C2 arylation of benzothiophene. A simple reuse of Ni@BpyMP-1 catalyst led only to traces of product. Since the molecular benzothiophene C-H arylation is proposed to occur through a redox pathway (believed to involve Ni(I)/Ni(III) species, even if a Ni(0)/Ni(II) redox catalysis cannot be ruled out),1 we also postulate an irreversible nickel oxidation as deactivation pathway in the heterogeneous system. In order to reactivate the Ni species, we thus tested reducing agents such as sodium borohydride (NaBH4). The TON reaches approx. 44 per run using 1wt%Ni@BpyMP-1 in the presence of NaBH4 (Figure 1c). After seven consecutive catalytic runs, a cumulative TON of 316 was reached. This corresponds to a total productivity of 12 grams of 2-phenylbenzothiophene per gram of catalyst.We demonstrate here the heterogeneously catalyzed direct and fully regioselective C2-H arylation of various het-eroarenes, including benzothiophene as an important building block for APIs. We also report the first proof-of-principle protocol for its efficient regeneration. The optimized heterogeneous catalytic system has been reused for at least seven times with a total TON of ca. 300 and a productivity of 12 grams of 2-phenylbenzothiophene per gram of catalyst without significant Ni leaching. The applicability of this novel heterogeneous system was further demonstrated by success-fully arylating other heterocycles like thiophenes, selenophene and indole. Taking into account their robustness and their potential processability, the porous organic polymers used as macroligands for molecular catalysts further pave the way to molecularly defined and robust heterogeneous systems for a more sustainable synthesis of fine chemicals.

To change the paradigm of molecular catalytic processes for fine chemical synthesis and green fuel production, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis. Having molecularly-defined active sites, porous macroligands have been found to drive the activity of heterogenized catalytic processes on a similar way as molecular ligands but with the advantage of the structuration in a three-dimensional framework and the confinement within a porous nanospace. We first demonstrated that a parameter defined at the molecular level, like the Hammett constant, can be applied at the scale of a porous materials to tune the productivity of heterogeneous catalyst. Following this principle, organometallic Rh molecular complexes embedded within porous organic polymer (POP) and metal-organic frameworks (MOF) used as macroligand showed a high productivity for the photoreduction of carbon dioxide into formic acid using visible light as sole energy source. Another generation of these heterogenous photocatalysts has been then designed to combine both the Rh catalytic site and a photosensitizer in a unique network. The superior productivity of this all-in-one catalytic system originated from a perfect interplay between the photosensitizer to the catalytic unit. Finally we applied our strategy to more complex Rh-based metal organic polyhedral (Rh-MOP) as catalytic building units. Rh-MOP gels showed the highest activity reported so far for CO2 to formic acid photoreduction using visible light, with a productivity of 3 g(formic acid)/g(catalyst)/h. The MOP gel assembly has been furthermore evidenced to have enhanced activity compared to the parent molecular MOP due to electronic effect of bridging linker.

The last decade has seen an unprecedented progress in the discovery of new functional porous materials as well as the prediction of their properties. While the reactivity and enantioselectivity of molecular chiral catalysts have been rationalized and ultimately predicted for liquid-phase homogeneous phase reactions, asymmetric transformations associated to the increasing sophistication of MOF-based heterogeneous catalysts structures render computational efforts challenging. Here, in the case of asymmetric catalysis, the role of the MOF in confining the catalyst and in sterically constraining the approach of the substrate at the catalytic site is discussed. The specificities of host-guest interactions in the heterogeneous MOF-based catalyst when compared to those of molecular homogeneous counterparts are highlighted. We will show that computational chemistry can explain and even predict the selectivity in confined asymmetric catalysis within a MOF [1].Computationally generated structures of Al-MIL-101-NH-Gly-Pro containing a benzene ruthenium complex as catalytically active site have been thoroughly analyzed for docking of prochiral substrate. The obtained data gave insights into enantioselective process at play inside the MOF and allowed to predict the selectivity of asymmetric transfer hydrogenation reaction catalyzed within the MOF.Experimentally, the heterogenization of a chiral benzene ruthenium molecular complex within the MIL-101-NH-Gly-Pro [2, 3] cavity allows a threefold enhancement of the selectivity in the catalyzed asymmetric transfer hydrogenation of acetophenone compared to homogenous analogue system. The excellent match between the computational outcomes and observed enantiomeric excesses provides a robust atomic-level rationale for the observed product selectivity.With these unpublished results, DFT-level computations supported by experimental data highlight the crucial role of the MOF as a macroligand [4] for the ruthenium catalyst to direct the enantioselectivity of the reaction. The molecular level understanding towards the prediction of structure-reactivity relationship in hybrid porous solids like MOF allows reaching the same level of rationalization in the design of heterogeneous catalyst than that developed for decades for molecular systems.[5]This work has been carried out within the French ANR projects HOPFAME (ANR-13-BS07-0002-01) and POMAC (ANR-18-CE07-0025-01).References1.J. Canivet et al. Chem. Sci. 11, 8800–8808 (2020).2.J. Bonnefoy et al., J. Am. Chem. Soc. 9409–9416 (2015).3.T.K. Todorova et al., Chem. Eur. J. 22, 16531–16538 (2016).4.F. M. Wisser et al. ACS Catal. 8, 1653–1661 (2018).5.J.P. Reid et al., Nat. Rev. Chem. 2, 290 (2018).

carbon footprint reduction. CO2, N2 , H2 and biomass can be key vector molecules to enable such renewable energy insertion in the value chain of process industry [1]. A frontier in catalysis connected with this challenge is the development robust and stable solid catalysts which can be integrated in 3D devices capable of harvesting renewable energy (be it a “green electron”[1b] or photon) to perform the targeted reductions. Mono-metallic atomically precise systems are emerging which contribute to such approach. Some recent research achievements around catalytic systems developed by surface organometallic chemistry will be presented here. Among them, one example based on the integration of well-defined rhodium-based catalytic system in microporous-based material for CO2 reduction [2a], with formate as the sole carbon-containing product which result more stable and selective than their homogenous counterpart while preserving the predictive structure-activity correlation known for the metal complexes in solution; one example on the usefulness of Atomic Layer Deposition to build BiVO4-based photoactive structures [2b] and one based on Covalent Triazine Frameworks (CTFs) [2c].ref:1. [a] Themed issue “Harvesting renewable energy with Chemistry” Green Chemistry, 19 (10), pages 2299-2464 (2017). [b] Quadrelli, E.A. Green Chemistry, 2016, 18, 328. [c] Centi, G.; Quadrelli, E. A. and Perathoner S., Energy Environ. Sci., 2013, 6, 1711-1731. 2 [a] F. M. Wisser, M. Duguet, Q. Perrinet, Ashta C. Ghosh, Marcelo Alves-Favaro, Yorck Mohr, Chantal Lorentz, Elsje Alessandra Quadrelli, Regina Palkovits, David Farrusseng, Caroline Mellot-Draznieks, Vincent de Waele, and Jérôme Canivet Angew. Chem. Int. Ed. 2020, 59,5116 –5122 DOI: 10.1002/anie.201912883 [b] K. R Tolod, T. Saboo; S. P. Hernández, H. Guzman, M. Castellino, R. Irani, P. Bogdanoff, F. F Abdi, E. A. Quadrelli, N. Russo Appl. Catl. A. 605, 117796 (2020) [2c] M. Alves Fávaro, D. Ditz, J. Yang,S. Bergwinkl, A. Ghosh, M. Stammler, C. LorentzJ. Roeser, E. A. Quadrelli, A. Thomas, R. Palkovits, J. Canivet, F. Wisser, ACS Applied Materials & Interfaces accepted (2022). https://chemrxiv.org/engage/chemrxiv/article-details/61b3b18d689c872488de8301

Metal-catalyzed hydroformylation reaction for the conversion of alkenes to aldehydes via C-C bond formation has been considered as one of the very important reaction for both industrial and academic research. On the other hand, molecularly-defined complexes can be efficiently heterogenized within the porous networks of MOFs without affecting neither their molecular nature nor their catalytic behavior. MOF as crystalline vessel for well-defined molecular species allows for benefiting from shaping and recycling ability inherent to the solid state as well as for molecular-scale interactions and reactivity unreachable under homogeneous liquid-state conditions. Phosphine MOF without oxidation and series of eight Rh-MOF catalysts with activity up to 2400 h-1 for ethylene hydroformylation towards propionaldehyde as sole carbon-containing product. Temperature and pressure dependent catalytic studies along with kinetics of the reaction have en-lighten more regarding the ethyelene hydroformylation with Rh-MOF catalysts. Combined experimental and computa-tional methods to unravel structure and evolution of Rh species within the MOF under catalysis conditions in line with molecular mechanism.Acknowledgments: This work has been carried out within the C123 project that has received funding from the European Union’s Horizon 2020 research and innovation program under Grant Agree-ment No. 814557. Authors are very grateful to C123 partners and in particular to Richard Heyn (Sintef, Norway) for fruitful discussion. The authors thank the IRCELYON scien-tific services.

SSCI-VIDE+ING+JEC:RRJ:BCH:FWI:EQD; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. To change the paradigm of molecular catalytic processes for fine chemical synthesis and green fuel production, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis.[1] Having molecularly-defined active sites, porous macroligands have been found to drive the activity and the selectivity of heterogenized catalytic processes on a similar way as molecular ligands but with the advantage of the structuration in a three-dimensional framework[2] and the confinement within a porous nanospace.[3] We first demonstrated that the design of highly efficient heterogeneous catalyst based on porous organic polymer (POP) and metal-organic frameworks (MOF) is driven by the Hammett parameter of bipyridine-chelating macroligand as demonstrated for the photoreduction of carbon dioxide, with turnover frequencies among the highest reported for heterogeneous photocatalytic formate production.[2,4] More recently, we showed that the heterogenization of a chiral benzene ruthenium molecular complex within the MIL-101-NH-Gly-Pro cavity allows a threefold enhancement of the selectivity in the catalyzed asymmetric transfer hydrogenation of ketone compared to homogenous analogue system.[3] The DFT-level computations supported by experimental data highlight the crucial role of the MOF as a macroligand for the ruthenium catalyst to direct the enantioselectivity of the reaction. In these two cases, accurate descriptor at the molecular level can be used to predict activity and selectivity of confined molecular catalysts within macroligands.References:1.F. M. Wisser, Y. Mohr, E. A. Quadrelli, J. Canivet, ChemCatChem 2020, 12, 1270–1275.2.F. M. Wisser, M. Duguet, Q. Perrinet, A. C. Ghosh, M. Alves‐Favaro, Y. Mohr, C. Lorentz, E. A. Quadrelli, R. Palkovits, D. Farrusseng, C. Mellot‐Draznieks, V. de Waele, J. Canivet, Angew. Chem. Int. Ed. 2020, 59, 5116–5122.3.J. Canivet, E. Bernoud, J. Bonnefoy, A. Legrand, T. Todorova, E. A. Quadrelli, C. Mellot-Draznieks, Chem. Sci. 2020, 11, 8800–8808.4.F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, Acs Catal. 2018, 8, 1653–1661.

SSCI-VIDE+ING+JEC; National audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. To change the paradigm of molecular catalytic processes for fine chemical synthesis and green fuel production, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis. Having molecularly-defined active sites, porous macroligands have been found to drive the activity and the selectivity of heterogenized catalytic processes on a similar way as molecular ligands but with the advantage of the structuration in a three-dimensional framework and the confinement within a porous nanospace. We first demonstrated that the design of highly efficient heterogeneous catalyst based on porous organic polymer (POP) and metal-organic frameworks (MOF) is driven by the Hammett parameter of bipyridine-chelating macroligand as demonstrated for the photoreduction of carbon dioxide, with turnover frequencies among the highest reported for heterogeneous photocatalytic formate production. More recently, we showed that the heterogenization of a chiral benzene ruthenium molecular complex within the MIL-101-NH-Gly-Pro cavity allows a threefold enhancement of the selectivity in the catalyzed asymmetric transfer hydrogenation of ketone compared to homogenous analogue system. The DFT-level computations supported by experimental data highlight the crucial role of the MOF as a macroligand for the ruthenium catalyst to direct the enantioselectivity of the reaction. In these two cases, accurate descriptor at the molecular level can be used to predict activity and selectivity of confined molecular catalysts within macroligands.See Wisser et al., ACS Catal. 2018, 8, 1653–1661; Wisser, et al., Angew. Chem. Int. Ed. 2020, 59, 5116–5122 and Canivet, et al., Chem. Sci. 2020, 11, 8800–8808.

SSCI-VIDE+ING+JEC:MAS:FWI:EQD; National audience; Using sunlight as a renewable source of energy to promote carbon dioxide (CO2) conversion is an interesting approach to address sustainable chemicals and fuels production as well as mitigation of climate change. However, in most photocatalytic systems, the utilization of a homogeneous photosensitizer represent a key limitation for long-term reactions due to its low stability. Therefore, novel, more efficient and stable photocatalyst materials and photocatalytic processes are required.Here, we present a strategy of structuration at the molecular-level photocatalytic systems, seeking for enhanced long-term stability. The integration of photo-active centers into a molecularly defined support improve their stability. Moreover, the incorporation of chelating moieties, such as bipyridine, offer a unique possibility for heterogenization of organometallic complex, profiting at the same time from enhanced selectivity of the molecular catalyst and easy handling and separation from its heterogeneous nature. Macroligands, a solid acting like the ligand in the corresponding molecular complex, is a key strategy to bridge the gap between homogeneous and heterogeneous catalysis. Porous organic polymers (POPs), e.g. conjugated microporous polymers are attracting a growing interest for this task [1]. The key of their success is the tunability of the polymer’s proprieties. By judiciously chosen the proper tailored precursor, it is possible to carefully control light absorption and porosity. In this context, POPs can be precisely designed in order to contain both, a photoactive moiety and chelating site for the heterogenization of molecular catalysts within the structure.In our all-in-one concept, a (Cp*)-Rhodium complex was heterogenized within different dye containing macroligands.[2] Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst during four days, without any changes in catalytic activity. In this contribution, we will demonstrate the benefit of covalent tethering of the two active sites into a single framework to play a key role in the visible light activation of the catalyst. The photoinduced electron transfer from the light harvesting moiety to the catalytic site will be discussed based on quantum mechanical calculations and in-situ ultrafast time-resolved spectroscopy. [2][1] Bonillo, B., Sprick, R. S. and Cooper, A. I. (2016), Tuning Photophysical Properties in Conjugated Microporous Polymers by Comonomer Doping Strategies. Chemistry of Materials, 28 (10), 3469-3480.[2] Wisser, F. M., Duguet, M., Perrinet, Q., Ghosh, A. C., Alves-Favaro, M., Mohr, Y., Lorentz, C., Quadrelli, E. A., Palkovits, R., Farrusseng, D., Mellot-Draznieks, C., De Waele, V. and Canivet, J. (2020), Molecular Porous Photosystems Tailored for Long‐Term Photocatalytic CO2 Reduction. Angew. Chem. Int. Ed. doi:10.1002/anie.201912883

SSCI-VIDE+ING+JEC:EQD; International audience; The last decade has seen an unprecedented progress in the discovery of new functional porous materials as well as the prediction of their properties. While the reactivity and enantioselectivity of molecular chiral catalysts have been rationalized and ultimately predicted for liquid-phase homogeneous phase reactions, asymmetric transformations associated to the increasing sophistication of MOF-based heterogeneous catalysts structures render computational efforts challenging. Here, in the case of asymmetric catalysis, the role of the MOF in confining the catalyst and in sterically constraining the approach of the substrate at the catalytic site is discussed. The specificities of host-guest interactions in the heterogeneous MOF-based catalyst when compared to those of molecular homogeneous counterparts are highlighted. We will show that computational chemistry can explain and even predict the selectivity in confined asymmetric catalysis within a MOF.Computationally generated structures of Al-MIL-101-NH-Gly-Pro containing a benzene ruthenium complex as catalytically active site have been thoroughly analyzed for docking of prochiral substrate. The obtained data gave insights into enantioselective process at play inside the MOF and allowed to predict the selectivity of asymmetric transfer hydrogenation reaction catalyzed within the MOF.Experimentally, the heterogenization of a chiral benzene ruthenium molecular complex within the MIL-101-NH-Gly-Pro [1, 2] cavity allows a threefold enhancement of the selectivity in the catalyzed asymmetric transfer hydrogenation of acetophenone compared to homogenous analogue system. The excellent match between the computational outcomes and observed enantiomeric excesses provides a robust atomic-level rationale for the observed product selectivity.DFT-level computations supported by experimental data highlight the crucial role of the MOF as a macroligand for the ruthenium catalyst to direct the enantioselectivity of the reaction. [3] The molecular level understanding towards the prediction of structure-reactivity relationship in hybrid porous solids like MOF allows reaching the same level of rationalization in the design of heterogeneous catalyst than that developed for decades for molecular systems.[4]This work has been carried out within the French ANR projects HOPFAME (ANR-13-BS07-0002-01) and POMAC (ANR-18-CE07-0025-01). [1] J. Bonnefoy et al., J. Am. Chem. Soc. 9409–9416 (2015). [2] T.K. Todorova et al., Chem. Eur. J. 22, 16531–16538 (2016). [3] J. Canivet et al. Chem. Sci. 11, 8800–8808 (2020). [4] J.P. Reid et al., Nat. Rev. Chem. 2, 290 (2018).

SSCI-VIDE+ING+FWI:DFA:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frame-works made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as bipyridines are widely used as chelating ligand for molecular catalysts.[1–4]Amongst the catalytic applications, photochemical reactions such as CO2 reduction are of great interest as routes to different value-added C1-molecules, which have high potential as renewable energy sources. Although many efforts on increasing the catalytic efficiency have been achieved, typical catalytic photosystems suffer from low long-term stability or selectivity. Here, we will present a set of fully heterogeneous photosystems for the photocatalytic reduction of CO2 using visible light in the absence of any external photosensitizer. In these materials, the light harvesting moieties are directly enchased in the material structure and tethered to the catalytically active rhodium complexes. These new types of heterogeneous photocatalysts allow a constant and efficient transformation of CO2 into formate with production rates of up to 700 µmol formate per gram of catalyst per hour without any deactivation for at least 4 days, a superior performance with respect to state of the art. We explain their superior performance by a combination of stable organic dyes used as photosensitizer under the visible light, a well-adapted electron density on the active site by a rational choice of the porous framework and an optimized charge separation. We will demonstrate, using in-situ transient spectroscopy, that upon metalation, the excited states of the fully heterogeneous photosystems are effectively quenched resulting in a decrease of their life-times. DFT calculations show that the LUMO of the fully heterogeneous photosystem is centered on the Rh-based catalyst. This allows for an efficient electron transfer from the photosensitizer to the catalytically active Rh and, as a result, helps to stabilize the charge-separated states. References[1]A. Corma, H. García, F. X. Llabrés i Xamena, Chem. Rev. 2010, 110, 4606–4655.[2]C. Kaes, A. Katz, M. W. Hosseini, Chem. Rev. 2000, 100, 3553–3590.[3]F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal. 2018, 8, 1653–1661.[4]F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem 2018, 10, 1778–1782.

SSCI-VIDE+ING+FWI:YMO:DFA:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frame-works made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as bipyridines are widely used as chelating ligand for molecular catalysts.[1–4]Amongst the catalytic applications, photochemical reactions such as CO2 reduction are of great interest as routes to different value-added C1-molecules, which have high potential as renewable energy sources. Although many efforts on increasing the catalytic efficiency have been achieved, typical catalytic photosystems suffer from low long-term stability or selectivity. Here, we will present a set of fully heterogeneous photosystems for the photocatalytic reduction of CO2 using visible light in the absence of any external photosensitizer. In these materials, the light harvesting moieties are directly enchased in the material structure and tethered to the catalytically active rhodium complexes. These new types of heterogeneous photocatalysts allow a constant and efficient transformation of CO2 into formate with production rates of up to 700 µmol formate per gram of catalyst per hour without any deactivation for at least 4 days, a superior performance with respect to state of the art. We explain their superior performance by a combination of stable organic dyes used as photosensitizer under the visible light, a well-adapted electron density on the active site by a rational choice of the porous framework and an optimized charge separation. We will demonstrate, using in-situ transient spectroscopy, that upon metalation, the excited states of the fully heterogeneous photosystems are effectively quenched resulting in a decrease of their life-times. DFT calculations show that the LUMO of the fully heterogeneous photosystem is centered on the Rh-based catalyst. This allows for an efficient electron transfer from the photosensitizer to the catalytically active Rh and, as a result, helps to stabilize the charge-separated states. References[1]A. Corma, H. García, F. X. Llabrés i Xamena, Chem. Rev. 2010, 110, 4606–4655.[2]C. Kaes, A. Katz, M. W. Hosseini, Chem. Rev. 2000, 100, 3553–3590.[3]F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal. 2018, 8, 1653–1661.[4]F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem 2018, 10, 1778–1782.

SSCI-VIDE+ING+FWI:JEC; International audience; 1.ScopePhotocatalytic CO2 reduction reactions have gained enormous interest as they offer highly sustainable routes for providing renewable fuels and small building blocks for chemicals. The direct transformation of CO2 into formic acid or formate gives access to promising hydrogen storage molecules currently discussed for fuel cell applications. In an ideal zero carbon emission process, the CO2 produced in the fuel cell will be again reduced into formate or formic acid.[1]For the photochemical reduction of CO2, different molecular or macromolecular homogeneous catalysts have been developed, showing high initial activities in the presence of an external photosensitizer.[2,3] However most of them undergo an irreversible deactivation upon catalytic cycles either by decomposition or intermolecular interactions.[4] Intermolecular interactions can be avoided by the heterogenization of the catalyst onto a solid microporous support. However, the heterogenization often results in an intrinsic reduction of the catalytic activity.[5] Understanding and overcoming this decrease in activity remains today a major challenge for chemists, as its reasons are not yet fully understood. 2.Results and discussion Here we present a series of heterogeneous catalysts based on metal-organic frameworks and microporous polymers for the photoreduction of CO2 into formate.[6] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range structure of the porous support. Electronic effects of the microporous ligand have been neglected so far. The rational design of heterogenized catalysts for the photoreduction of CO2 is demonstrated here with turnover frequencies (TOF)s up to 28 h−1, in the presence of a homogeneous photosensitizer.[6]We will also present completely heterogeneous photocatalysts to overcome the current limitation of photodegradation of the photosensitizer. In these systems both the photo-sensitizer and the catalyst are integrated into the same framework, either co-immobi-lized inside the pore or covalently tethered to each other in the backbone. In the first approach, the pores are used as nanoreactors, as the catalyst and photosensitizer are co-confined into the cavity’s nanospace and enable molecular catalysis in a heterogeneous manner.[7] This approach allows to develop a photocatalytic system that completely suppresses the hydrogen evolution typically observed as a side reaction. Concerning the second approach, different organic photosensitizers will be evaluated in terms of their light absorption properties and the catalytic activities of the resulting fully heterogeneous photo-system (Figure 1). These new types of heterogeneous photocatalysts allow for a constant and efficient transformation of CO2 into formate without any deactivation for at least 48 h. The reasons for their superior perfor-mance will be discussed.References[1]M. Grasemann, G. Laurenczy, Energy Environ. Sci. 2012, 5, 8171.[2]Y. Yamazaki, H. Takeda, O. Ishitani, J. Photochem. Photobiol. C Photochem. Rev. 2015, 25, 106–137.[3]N. Elgrishi, M. B. Chambers, X. Wang, M. Fontecave, Chem. Soc. Rev. 2017, 46, 761–796.[4]T. Nakajima, Y. Tamaki, K. Ueno, E. Kato, T. Nishikawa, K. Ohkubo, Y. Yamazaki, T. Morimoto, O. Ishitani, J. Am. Chem. Soc. 2016, 138, 13818–13821.[5]E. A. Quadrelli, J. M. Basset, Coord. Chem. Rev. 2010, 254, 707–728.[6]F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal. 2018, 8, 1653–1661.[7]X. Wang, F. M. Wisser, J. Canivet, M. Fontecave, C. Mellot-Draznieks, ChemSusChem 2018, 11, 3315–3322.

SSCI-VIDE+ING+JEC:FWI:DFA; International audience; The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates.[1,2]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity.The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[1] among the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2] The principle of macroligand rational design will be shown to be further extended to a wide range of catalytic reactions for fine chemical synthesis and energy.This work is carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996.

SSCI-VIDE+ING+FWI:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as bipyridines are widely used as chelating ligand for molecular catalysts.[1]Amongst the catalytic applications, photochemical carbon dioxide reduction is of tremendous importance as routes to renewable energy sources. Here we present a series of heterogeneous catalysts based on metal-organic frameworks and microporous polymers used as macroligands for heterogenized organometallic complexes.[2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts is demonstrated here for the photoreduction of carbon dioxide into formate with turnover frequencies up to 28 h−1, in the presence of a homogeneous photosensitizer.[2]We will also present completely heterogeneous photocatalysts to overcome the current limitation of photodegradation of the light harvesting moiety. In these systems both the photosensitizer and the catalyst are integrated into the same framework, either covalently to the backbone or by co-immobilized inside the pores. In the later case, the pores are used as nanoreactors, as the catalyst and photosensitizer are co-confined into the cavity’s nanospace and enable molecular catalysis in a heterogeneous manner.[3] This approach allows to develop a photocatalytic system that completely suppresses the hydrogen evolution typically observed as a side reaction. Finally, different photo-sensitizers will be evaluated in terms of their light absorption properties and the resulting catalytic activities.References:[1] a) A. Corma, H. García, F. X. Llabrés i Xamena Chem. Rev. 2010, 110, 4606-4655; b) C. Kaes, A. Katz, M. W. Hosseini Chem. Rev. 2000, 100, 3553-3590.[2] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet ACS Catal. 2018, 8, 1653-1661. [3] X. Wang, F. M. Wisser, J. Canivet, M. Fontecave, C. Mellot-Draznieks, ChemSusChem, 2018, 11, 3315-3322.

SSCI-VIDE+ING+YRX:YMO:FWI:DFA:JEC; National audience; Today, C-H activation processes are largely used to simplify the synthesis of pharmaceuticals, natural products, polymers. Indeed, most of them are based on (hetero)aryl cores, such as indoles, pyrroles, pyrimidines, tetrazoles… . 1 Their synthesis involves at least one catalytic step based on traditional carbon-carbon coupling (Heck, Suzuki…). Usually, homogeneous catalysis with Pd is preferred. However, several issues remain such as the lack of selectivity, the presence of metal residues, ligand stability and, finally, homogeneous catalysts cannot be recovered and/or recycled. Heterogenous catalysts with single site isolated catalytic species might circumvent these issues. In this context, we decided to develop imidazolium based microporous polymer (IMP) (Figure 1) as solid macroligand for the heterogenization of C-H arylation molecular catalysts.Figure 1: Synthesis of Imidazolium based microporous polymer (IMP-1) and conditions of Pd(OAc)2 loading inside IMP-1The synthesis of the polymer is achieved with 70 % yield as a yellow powder.2,3 The polymer was characterized by IR spectroscopy, N2 adsorption isotherm, solid state NMR spectroscopy. Then metal salt (M) as catalyst precursor is loaded inside the polymer in the presence of KHMDS and toluene. M@IMP-1 is obtained with quantitative yield as a yellow porous solid. Thus IMP can serve as platform by designing them with different NHC and metals to reach several applications in different catalytic processes, and especially in C-H arylation of various heteroarenes as demonstrated here with 100% regioselectivity and yield as high as those reached with molecular analogues (TON up to 100). These novel heterogeneous catalysts will avoid metal leaching, increase catalytic activity and selectivity and will allow for recyclability and implementation in flow processes. This work has been carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996.(1) Kaushik, N.; Kaushik, N.; Attri, P.; Kumar, N.; Kim, C.; Verma, A.; Choi, E. Molecules 2013, 18 (6), 6620–6662. (2) Wisser, F. M.; Berruyer, P.; Cardenas, L.; Mohr, Y.; Quadrelli, E. A.; Lesage, A.; Farrusseng, D.; Canivet, J. ACS Catal. 2018, 8 (3), 1653–1661. (3) Wisser, F. M.; Mohr, Y.; Quadrelli, E. A.; Farrusseng, D.; Canivet, J. ChemCatChem 2018, 10 (8), 1778–1782.

SSCI-VIDE+ING+YMO:JEC:FWI:DFA; International audience; At the molecular scale, the integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1,2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity as exemplified in two reactions. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The gap between molecular and heterogeneous catalysis has never been so close to being bridged. This work is carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996. H-CCAT aims at the large scale production of MOF catalysts and at their use in the industrial production of pharmaceuticals.[1] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal., DOI: 10.1021/acscatal.7b03998 (2018)[2] F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem, DOI: 10.1002/cctc.201701836 (2018)

SSCI-VIDE+ING+JEC:FWI:DFA; International audience; 1. Introduction Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1,2]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. 2. Results & DiscussionWe show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. (Figure 1). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[1] among the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2] Figure 1. Hammett parameter as universal descriptor: Linear correlation between TOF and electronic properties of the macroligand.The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. 4. ConclusionsThe results obtained on two different reaction with six different heterogenous catalysts evidence the linear correlation between the activity of heterogenized RhCp*-based catalyst and the local electron density around this isolated active site. This linear relationship make it possible to predict the catalytic activity of such a system based on the local electronic contribution of the ligand, as described by the Hammett constant. Moreover, the established correlation between the Hammett constant and the catalytic activity will make it possible to discriminate if heterogeneous catalyst performance is mainly driven by local catalyst activation or by diffusion inside the porous support under operating conditions.The rational design of polymeric platforms envisioned as macroligands and guided by the Hammett parameter will enable the production of ever better-performing microporous solid-based heterogeneous catalysts. The gap between molecular and heterogeneous catalysis has never been so close to being bridged. This work has been carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under the grant agreement No 720996.

SSCI-VIDE+ING+FWI:JEC:DFA; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frame-works made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as bipyridines are widely used as chelating ligand for molecular catalysts.[1]Amongst the catalytic applications, photochemical carbon dioxide reduction is of tremendous importance as routes to renewable energy sources. Here we present a series of heteroge-neous photocatalysts based on metal-organic frameworks and microporous polymers used as macroligands for heterogenized organometallic complexes.[2] We show that both homo-geneous and heterogenized catalysts follow the same linear correlation between the elec-tronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. This is demonstrated here for the Rh-catalyzed photoreduction of carbon dioxide into formate with turnover frequencies (TOF) up to 28 h−1, the highest TOFs reported so far for heterogeneous photocatalytic formate production.[2]We will also present completely heterogeneous photocatalysts to overcome the current limi-tation of photodegradation of the light harvesting moiety. In these systems both the photo-sensitizer and the catalyst are integrated into the same framework,[3] thus increasing the long-term stability of the catalyst. In addition, different photosensitizers will be evaluated in terms of their light absorption properties and the resulting catalytic activities.References:[1] a) A. Corma, H. García, F. X. Llabrés i Xamena Chem. Rev. 2010, 110, 4606-4655;b) C. Kaes, A. Katz, M. W. Hosseini Chem. Rev. 2000, 100, 3553-3590.[2] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet ACS Catal. 2018, 8, 1653-1661.[3] X. Wang, F. M. Wisser, J. Canivet, M. Fontecave, C. Mellot-Draznieks, ChemSusChem, DOI: 10.1002/cssc.201801066

SSCI-VIDE+ING+YMO:FWI:DFA:JEC; International audience; The Young Investigator Symposium is an emerging tradition of the MOF conference, and is a high-profile opportunity for students, postdoctoral researchers, and young faculty members to showcase their research before a diverse and global audience. This edition of the one-day symposium will feature a series of short, invited and contributed presentations and opportunities for informal discussions throughout the day.

SSCI-VIDE+ING+JEC; International audience; At the molecular scale, the integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1,2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity as exemplified in two reactions. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The gap between molecular and heterogeneous catalysis has never been so close to being bridged. This work is carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996. H-CCAT aims at the large scale production of MOF catalysts and at their use in the industrial production of pharmaceuticals.[1] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal., DOI: 10.1021/acscatal.7b03998 (2018)[2] F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem, DOI: 10.1002/cctc.201701836 (2018)

SSCI-VIDE+ING+KBA:JEC; International audience; Summary: Catalytic Methane Partial Oxidation to Methanol reaction represents a big challenge for both industrial and academic research because i) it is a concrete, sustainable solution to GHGs emissions, whose Methane is a major actor, ii) it is difficult to achieve hitherto high selectivity of the desired oxygenated intermediates and low COx products, iii) methanol is a clean and high-added value fuel source, whose market is in continuous expansion[1]. Among the low T (< 300°C) and pressure (atmospheric) catalytic routes, a valuable approach is the use of single-component catalysts which mimic the Methane Monooxygenase (MMO) enzyme structures, consisting in binuclear centers of Fe or Cu, that so far have been recreated in zeolites to benefit of their greater external surface area[2]. Nevertheless, the major drawbacks in using any zeolite are related to the hydrophilicity of the support, which is detrimental for desorption of products, and the need of a looping system to increase methane conversion which includes solvent extraction, recycling of unreacted methane, and sites reactivation. To circumvent some of these issues, the anchorage of the active metal into a Metal-Organic Framework (MOF) by post-synthetic treatment has been recently reported[3], demonstrating the potential of such class of materials, although a rational design of performing MOF-based catalyst is still needed. In this work, the recreation of the enzyme type structures with atomically dispersed atoms, specific coordination, and controlled loading has been achieved i) by substitution of Zn nodes with Fe inside hydrophobic zeolite imidazolate frameworks (ZIF) (Figure 1), or ii) by Cu immobilization in UiO-66. These strategies lead to isolated sites onto a porous support which itself acts as a transient nanoreactor to achieve higher methanol selectivity. The physico-chemical properties of each material synthesized have been determined by SEM-EDX, XRD, N2 sorption isotherms, and XPS techniques. Their catalytic properties have been then evaluated in Methane Partial Oxidation reaction under mild conditions (130-170 °C, 0.5-4 bar) using a CH4/O2 mixture (2-3/1 v/v%) in a Plug Flow Reactor configuration, and compared with those of Fe/ and Cu/ ZSM-5 as reference catalysts.

SSCI-VIDE+ING+YMO:FWI:DFA:JEC; International audience; None

SSCI-VIDE+ING+FWI:YMO:DFA:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1]Amongst the catalytic applications, photochemical CO2 reduction is of tremendous importance as routes to renewable energy sources. Here we present series of heterogeneous photocatalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes.[2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity (Scheme 1). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. This is demonstrated here for the Rh-catalyzed photoreduction of carbon dioxide into formate with turnover frequencies (TOF) up to 28 h−1, the highest TOFs reported so far for heterogeneous photocatalytic formate production.[2]We will also present different strategies for preparing completely heterogeneous photo-catalytic systems to overcome the current limitation of photodegradation of the light harvesting moiety. Here we consider systems where both the photosensitizer and the catalyst are integrated in the same framework,[3] thus increasing the long-term stability of the catalyst.References: [1] a) A. Corma, H. García, F. X. Llabrés i Xamena Chem. Rev. 2010, 110, 4606-4655; b) C. Kaes, A. Katz, M; W. Hosseini Chem. Rev. 2000, 100, 3553-3590.[2] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet ACS Catal. 2018, 8, 1653-1661.[3] X. Wang, F. M. Wisser, J. Canivet, M. Fontecave, C. Mellot-Draznieks, submitted for publication.

SSCI-VIDE+ING+KBA:JEC; International audience; Summary: Catalytic Methane Partial Oxidation to Methanol reaction represents a big challenge for both industrial and academic research because i) it is a concrete, sustainable solution to GHGs emissions, whose Methane is a major actor, ii) it is difficult to achieve hitherto high selectivity of the desired oxygenated intermediates and low COx products, iii) methanol is a clean and high-added value fuel source, whose market is in continuous expansion[1]. Among the low T (< 300°C) and pressure (atmospheric) catalytic routes, a valuable approach is the use of single-component catalysts which mimic the Methane Monooxygenase (MMO) enzyme structures, consisting in binuclear centers of Fe or Cu, that so far have been recreated in zeolites to benefit of their greater external surface area[2]. Nevertheless, the major drawbacks in using any zeolite are related to the hydrophilicity of the support, which is detrimental for desorption of products, and the need of a looping system to increase methane conversion which includes solvent extraction, recycling of unreacted methane, and sites reactivation. To circumvent some of these issues, the anchorage of the active metal into a Metal-Organic Framework (MOF) by post-synthetic treatment has been recently reported[3], demonstrating the potential of such class of materials, although a rational design of performing MOF-based catalyst is still needed. In this work, the recreation of the enzyme type structures with atomically dispersed atoms, specific coordination, and controlled loading has been achieved i) by substitution of Zn nodes with Fe inside hydrophobic zeolite imidazolate frameworks (ZIF) (Figure 1), or ii) by Cu immobilization in UiO-66. These strategies lead to isolated sites onto a porous support which itself acts as a transient nanoreactor to achieve higher methanol selectivity. The physico-chemical properties of each material synthesized have been determined by SEM-EDX, XRD, N2 sorption isotherms, and XPS techniques. Their catalytic properties have been then evaluated in Methane Partial Oxidation reaction under mild conditions (130-170 °C, 0.5-4 bar) using a CH4/O2 mixture (2-3/1 v/v%) in a Plug Flow Reactor configuration, and compared with those of Fe/ and Cu/ ZSM-5 as reference catalysts.

SSCI-VIDE+ING+JEC:FWI:DFA; International audience; The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates.[1-4]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,1 among the highest reported for heterogeneous photocatalytic CO2 reduction to formate [1] and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2]References: 1.F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal. 2018, DOI: 10.1021/acscatal.7b03998.2.F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem 2018, DOI: 10.1002/cctc.201701836R.3.J. Canivet, S. Aguado, Y. Schuurman, D. Farrusseng, J. Am. Chem. Soc. 2013, 135, 4195.4.M. B. Chambers, X. Wang, N. Elgrishi, C. H. Hendon, A. Walsh, J. Bonnefoy, J. Canivet, E. A. Quadrelli, D. Farrusseng, C. Mellot-Draznieks, M. Fontecave, Chemsuschem 2015, 8, 603.

SSCI-VIDE+ING+JEC; National audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1,2]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. As host for molecular Rh-based bypiridine catalysts, we prepared porous solids, which are bpy-containing MOF, namely UiO-67 and MOF-253, and four newly synthesized porous polymers. As shown in the Figure 1, these platforms present different Hammet constant at the meta-position of the bpy ligand. Figure 1. Representatives meta substituted 2,2'-bipyridine ligands embedded in MOF or CMP materials studied herein (σm = Hammett constant).We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity (Figure 2). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[1] among the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2] Figure 2. Linear correlation between TOF and electronic properties of the macroligand.The results obtained on two different reaction with six different heterogenous catalysts evidence the linear correlation between the activity of heterogenized RhCp*-based catalyst and the local electron density around this isolated active site. This linear relationship make it possible to predict the catalytic activity of such a system based on the local electronic contribution of the ligand, as described by the Hammett constant. The rational design of polymeric platforms envisioned as macroligands and guided by the Hammett parameter will enable the production of ever better-performing microporous solid-based heterogeneous catalysts. The gap between molecular and heterogeneous catalysis has never been so close to being bridged. References[1] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal., 8 (2018) 1653.[2] F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem, 10 (2018) 1778.

SSCI-VIDE+ING+JEC; National audience; The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates.[1,2]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[1] among the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2][1]. F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal. 2018, 8, 1653-1661.[2]. F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem 2018, DOI: 10.1002/cctc.201701836.

SSCI-VIDE+ING+JEC:FWI:YMO:YKH:DFA; National audience; At the molecular scale, the integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1,2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity (Figure 1). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. Thus the gap between molecular and heterogeneous catalysis has never been so close to being bridged. This work is carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 720996. H-CCAT aims at the large scale production of MOF catalysts and at their use in the industrial production of pharmaceuticals.Towards industrialization, we also worked at developing a production pilot line of MOF of 150 kg/day (Figure 2) which also includes an extrusion shaping line for the production of 1-5mm pellets. In contrast with usual laboratory MOF synthesis which uses organic solvent, the synthesis and shaping processes exclusively use water which enables their application in air purification devices. We will show that thermal, chemical and mechanical stability criteria are fulfilled for application in individual protective filter (face mask). For example, pellets of MOF outperformed commercial benchmark adsorbents for ammonia air purification (3M and Norit) in all conditions, especially in dry conditions, for which the commercial adsorbents suffered impaired ammonia uptake and shortened service life. This work is carried out within the ProDIA project, which has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No. 685727.[1] F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet, ACS Catal., DOI: 10.1021/acscatal.7b03998 (2018)[2] F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet, ChemCatChem, DOI: 10.1002/cctc.201701836 (2018)

+ING+FWI:YMO:LCS:DFA:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes.[2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity (Scheme 1). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules.[2a] The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[2a] the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2b] References: [1] a) A. Corma, H. García, F. X. Llabrés i Xamena Chem. Rev. 2010, 110, 4606-4655; b) C. Kaes, A. Katz, M; W. Hosseini Chem. Rev. 2000, 100, 3553-3590.[2] a) F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet submitted for publication; b) F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet ChemCatChem accepted for publication.

+ING+FWI:YMO:LCS:DFA:JEC; International audience; Heterogeneous catalysis allows to circumvent the problem of separation from the products and to simplify the recyclability of the catalyst. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge.[1] In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-organic frameworks and purely organic microporous polymers are promising candidates.[2] In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[3]We present novel bipyridine containing microporous polymers as a promising class of host materials for catalytically active metal complexes for CO2 reduction into value-added C1-molecules and fine chemicals synthesis such as transfer hydrogenation reaction. Their outstanding stability, tunability and swelling properties make these microporous polymers ideal supports for heterogenization of molecular catalysts. The active metal center, for instance organometallic rhodium complexes, can easily be integrated into the host by post-synthetic infiltration with a suitable precursor. For a rhodium loading of 1.6 wt%, a well-balanced equilibrium between number of active centers, remaining porosity, flexibility and thus accessibility of the active centers and catalytic performance was achieved.[4] Using this catalyst in CO2 photoreduction reaction turnover numbers (up to 113) and turnover frequencies (up to 28 h-1) are the highest reported so far for heterogenized catalysts and are very similar to that of the homogeneous analogs. For the transfer hydrogenation reaction of α-aryl ketones TOF of up to 3.3 h-1were achieved.[4]Here, we will demonstrate that the Hammett parameter – well established in molecular chemistry and homogeneous catalysis[5] – is also an appropriate descriptor for heterogenized organometallic catalytic centers within metal-organic frameworks and microporous polymers. In all reactions investigated, the catalytic activity of the heterogenized catalysts is only driven by the local electron density around the isolated active site and thus correlates with the Hammett constant of the bipyridine substituents. We will show how the rational design of active centers can be guided by the Hammett parameter allowing to optimize the performance of the heterogeneous catalysts. In addition, the use of Hammett plots – representing the activity as a function of the host’s Hammett constant – in combination with other characterization techniques allows to identify diffusion limitations within catalysts.References[1]a) M. P. Conley and C. Copéret, Top. Catal., 2014, 57, 843-851; b) L.-N. He, J.-Q. Wang and J.-L. Wang, Pure Appl. Chem., 2009, 81, 2069-2080.[2] a) T. Islamoglu, et al., Acc. Chem. Res. 2017, 50 (4), 805-813; b) N. B. McKeown, P. M. Budd, Chem. Soc. Rev. 2006, 35 (8), 675-683; c) S. M. Rogge, et al., J. Chem. Soc. Rev. 2017, 46, 3134-3184; d) P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem., Int. Ed. 2008, 47, 3450-3453.[3]C. Kaes, A. Katz, M. W. Hosseini, Chem. Rev. 2000, 100 (10), 3553-3590.[4]F. M. Wisser, et al. 2 papers submitted for publication.[5]C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91 (2), 165-195.

SSCI-VIDE+ING+JEC:FWI:DFA; International audience; The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates.[1,2]Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity.The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[1] among the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2]This work is carried out within the H-CCAT project that has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 720996.

SSCI-VIDE+ING+YMO:FWI:DFA:JEC; International audience; Heterobiaryl species are omnipresent in natural products and pharmaceuticals. Theirsynthesis often involves catalytic steps based on traditional homogeneous carbon-carboncoupling reactions.[1] Only in the last decade, the activation of aromatic C-H bonds has beentackled, leading to reduced synthetic steps and an improved atom economy.[2] Nevertheless,on an industrial scale metal residues from homogeneous catalysts complicate the productpurification and can be deleterious for subsequent synthetic steps. Heterogeneous catalysismight overcome the issue of metal contamination by enabling a mechanical separation of thecatalyst from the product. One possible strategy for heterogeneous catalyst design involvesin the integration of a well-defined molecular catalyst into a solid support.[3] This isolation ofcatalytically active sites from one another prevents possible multimetallic decomposition andthus favors the maintenance of optimal catalytic activity.In this perspective, porous frameworks[4] made by the repetition of a coordinating motif, suchas bipyridine appear to be ideal candidates for the heterogenization of molecular catalysts.Here we present a series of heterogeneous single-site catalysts based on microporousmaterials.[5][6] These novel catalysts are able to catalyze the direct arylation (C-H activation)of heteroaromatics with yields of up to 80% while keeping their overall structure and porosityintact. Leaching tests confirm the heterogeneous nature of the catalyzed reactions.

SSCI-VIDE+ING+FWI:JEC:DFA; International audience; In the past decade, microporous polymers, including both porous organic polymers and metal-organic frameworks (MOFs), have received increasing attention as they combine the advantages of high surface area and high pore volume with tunable structures and easy functionalization. The materials are well suited for technologically important applications such as gas storage and gas separation. They also have a high potential in some of the most challenging areas of chemical research, including heterogeneous catalysis, drug delivery or sensing. Amongst the catalytic applications, photochemical reactions such as water splitting and CO2 reduction are of tremendous importance as routes to renewable energy sources.[1] Recently our group reported the incorporation (heterogenization) of a rhodium based catalyst for the photochemical CO2 reduction within the MOF UiO-67. Using this catalyst, formate was obtained as the only carbon-containing product with a turnover number of ~25 after 4 h.[2] In this contribution we present novel bipyridine containing porous organic polymers as promising class of host materials for catalytically active rhodium complexes for carbon dioxide reduction. The active rhodium center can easily be integrated into the host by post-synthetic infiltration with a suitable precursor. The integration into the flexible porous polymer allows for a good accessibility of the active centers. Furthermore, the catalyst remains stable under the basic conditions of the photocatalysis and the productivity of formate remains constant over at least five cycles. The porous organic polymers-based catalysts exhibit high production rates R of formate. The R, TON and TOF values exceeded the best literature-known heterogeneous systems under similar conditions by at least one order of magnitude (up to R 3.7 ± 0.2 mmol/h/gcat as compared to < 0.5 mmol/h/gcat[2-3]). Literature:[1]a) P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem., Int. Ed. 2008, 47, 3450-3453; b) D. Wu, F. Xu, B. Sun, R. Fu, H. He, K. Matyjaszewski, Chem. Rev. 2012, 112, 3959-4015; c) J. L. White, M. F. Baruch, J. E. Pander Iii, Y. Hu, I. C. Fortmeyer, J. E. Park, T. Zhang, K. Liao, J. Gu, Y. Yan, T. W. Shaw, E. Abelev, A. B. Bocarsly, Chem. Rev. 2015, 115, 12888-12935; d) H. Zhang, G. Liu, L. Shi, H. Liu, T. Wang, J. Ye, Nano Energy 2016, 22, 149-168.[2]M. B. Chambers, X. Wang, N. Elgrishi, C. H. Hendon, A. Walsh, J. Bonnefoy, J. Canivet, E. A. Quadrelli, D. Farrusseng, C. Mellot-Draznieks, M. Fontecave, ChemSusChem 2015, 8, 603-608.[3]a) Y. Lee, S. Kim, H. Fei, J. K. Kang, S. M. Cohen, Chem. Commun. 2015, 51, 16549-16552; b) T. Kajiwara, M. Fujii, M. Tsujimoto, K. Kobayashi, M. Higuchi, K. Tanaka, S. Kitagawa, Angew. Chem., Int. Ed. 2016, 55, 2697-2700.

SSCI-VIDE+ING+FWI:JEC:DFA; International audience; In the past decade, microporous polymers have received increasing attention as they combine the advantages of high surface areas and high pore volumes with tunable structures and functionalities.[1] The materials are well suited as support for molecular catalysts, circumventing the separation problem of catalyst and products and simplifying the recyclability of the catalyst (heterogenization). Among the possible catalytic applications, photochemical water splitting or CO2 reduction are of tremendous importance as routes to renewable energy vectors.[2] The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge.[3]We present novel bipyridine containing microporous polymers as a promising class of host materials for catalytically active rhodium complexes for CO2 reduction into value-added C1-molecules. Their outstanding stability, tunability and swelling properties make these microporous polymers ideal supports for heterogenization of molecular catalysts. The active rhodium center can easily be integrated into the host by post-synthetic infiltration with a suitable precursor. For a rhodium loading of 1.6 wt%, a well-balanced equilibrium between number of active centers, remaining porosity, flexibility and thus accessibility of the active centers and catalytic performance was achieved, resulting in a formate production rate as high as 4.2 ± 0.1 mmol/h/gcat. Turnover numbers (up to 113) and turnover frequencies (up to 28 h-1) are the highest reported so far for heterogenized catalysts and are very similar to that of homogeneous analogs.We will show that the catalytic activity of the heterogenized rhodium catalysts is driven by the local electron density around the isolated active site and thus correlates with the Hammett constant of the bipyridine substituents. The overall structure and especially the conjugation of the polymeric host do not play a crucial role on the activity. We will demonstrate how the rational design of active centers can be guided by the Hammett parameter allowing to optimize the performance of the heterogeneous catalysts.Literature:[1]a) P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem., Int. Ed. 2008, 47, 3450-3453; b) D. Wu, et al., Chem. Rev. 2012, 112, 3959-4015. [2]a) G. Centi, E. A. Quadrelli and S. Perathoner, Energy Environ. Sci. 2013, 6, 1711-1731; b) J. L. White, et al., Chem. Rev. 2015, 115, 12888-12935; c) H. Zhang, et al., Nano Energy 2016, 22, 149-168; d) N. Chaoui, et al. Chem. Soc. Rev., 2017, DOI: 10.1039/c7cs00071e.[3]a) M. P. Conley and C. Copéret, Top. Catal., 2014, 57, 843-851; b) L.-N. He, J.-Q. Wang and J.-L. Wang, Pure Appl. Chem., 2009, 81, 2069-2080

SSCI-VIDE+ING+JEC:FWI:DFA; International audience; In the rush to innovation in Metal-Organic Frameworks, new methodologies have emerged in order to characterize ever more sophisticated materials that embed sometimes several different functional groups (chiral, organometallics, luminescent,…) in a single crystalline structure.Cutting-edge spectroscopic techniques, even combined with DFT calculations, have been successfully applied to the characterization of MOF materials containing multiple functionalities gathered in a unique framework.[1]Since the early 1980s, photoacoustic Fourier transform infrared spectroscopy (PA FT-IR) has been the subject of numerous technological evolutions, especially in sound collection.[2] Beyond its application in biomedical imaging, this technique has already been used to analyze inorganic rough surfaces and gases.[3]Here we present for the first time the correlation between the sound produced by IR-illuminated MOFs and the organic composition of their mixed-linker frameworks. We recently reported the use of azido-to-amino turn-on luminescence of a MOF upon sulfide exposure for the sensing of H2S as biomarker in physiological media.[4] The amino content in the amino/azido-MOF, after exposure of the pure azido, was directly linked to the sulfide concentration, used as biomarker for non-communicable diseases, of the analyzed biological sample solution. Similarly, we explore herein the different photoacoustic response of MOF-N3 and MOF-NH2, in order to ultimately determine the N3-to-NH2 molecular ratio in mixed-linker MOF powders.Furthermore, the sensitivity determined for the detection of amino content in an azido-MOF matrix is two orders of magnitude higher using PA FT-IR than using classic IR spectroscopy. The first sound collection from IR-illuminated mixed-linker MOFs allows determining their organic composition (i) in the solid state, (ii) rapidly and (iii) without specific sample preparation with outstanding sensitivity. This opens appealing new perspectives for the rapid characterization of libraries of multifunctional hybrid materials as well as for the use of MOFs in compact sensing devices.[1] Rossini et al. Angew. Chem. Int. Ed. 2012, 51, 123; Todorova et al. Chem. Eur. J. 2016, 22, 16531; Kong et al. Science 2013, 341, 882; Katzenmeyer et al. Angew. Chem. Int. Ed. 2014, 53, 2852.[2] Kuusela et al. Appl. Spectrosc. Rev. 2007, 42, 443[3] Wang et al. Nat. Photon. 2009, 3, 503 ; Wang et al. Nat. Methods 2016, 13, 627; Michaelian, K. H. Photoacoustic IR Spectroscopy: Instrumentation, Applications and Data Analysis, 2nd, Revised and Enlarged Edition; Wiley-VCH, 2010[4] Legrand et al. ChemNanoMat 2016, 2, 866-872.

SSCI-VIDE+ING+JDH:JEC:DFA; National audience; Typically, Metal-Organic Frameworks (MOFs) are prepared as sparse powders, thus showing rather low volumetric uptakes. However, in most applications restraints are dictated by the available volume. Therefore, a densification step appears necessary to make MOFs competitive against usual porous materials. Yet, substantial collapse of the structure, formed via coordination bonds, usually occurs during compression.We recently looked at the densification of several industrially-relevant MOFs: HKUST-1, and the isostructural series UiO-66, UiO-66-NH2, and UiO-67. Herein, we present the use of a R&D tableting robot to evaluate the impact of compression on the structural and textural properties of the resulting tablets, aiming at the best compromise between the tablets porosity and density. A slow densification allowed us to maintain most of the initial structure, as proved by XRD and N2 physisorption. We also mixed HKUST-1 powder with up to 2wt% of graphite to investigate its potential to minimize the effect of compression. Finally, we challenged the stability of our tablets after four months in standard room conditions.

SSCI-VIDE+ING+JEC:DFA; International audience; 1. Introduction The four major non-communicable diseases (NCDs, ie cardiovascular diseases, cancer, chronic respiratory diseases and diabetes) involve a variation of H2S concentration in blood. Indeed, H2S is the 3rd endogenously generated gaseous signaling compound and it’s involved in the biological systems under physiological and pathological conditions. The development of accurate point-of-care testing for H2S blood concentration will allow early diagnosis avoiding millions of deaths every year.2. Results and discussion We present a tailored MOF solid coupled for the first time with a femtosecond (fs)-pulse laser irradiation protocol to achieve the rapid in vitro detection of nanomolar sulfide in serum solutions. Three different MOF platforms are investigated here, namely MIL-68, MIL-101 and UiO-66. The detection is based on azido to amino turn on fluorescence upon H2S exposure.Our azido-modified Al-MIL-101 is thus an efficient sensor for sulfide in biologically relevant media, reaching the 100 nM detection limit under laser excitation. This result is a three order of magnitude sensitivity increase with respect to previously reported fluorescent azido-MOF which detected tens to hundreds micromolar sulfide under lamp excitation. Reasons of the superiority of our laser-based system are also discussed. 3. Conclusions In conclusion, the Al-MIL-101-based sensor allows reaching sulfide quantification in physiological solutions after only minutes of exposure in the micro- to nanomolar range for endogenous H2S concentrations. Through the adequate tuning of irradiation protocol, the rational selection of ligand-centered emission paves the way to MOF-based device construction by design, the hybrid solid capacity being driven by an almost infinite library of organic chromophore ligands.This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 685727See Legrand, A.; Pastushenko, A.; Lysenko, V.; Geloen, A.; Quadrelli, E.A.; Canivet, J.; Farrusseng, D., ChemNanoMat 2016, 2, 866-872 (Cover Picture)

SSCI-VIDE+ING+JEC:DFA; International audience; 1. Introduction According to the World health organization, the four major non-communicable diseases (NCDs, ie cardiovascular diseases, cancer, chronic respiratory diseases and diabetes) are responsible for 82% of NCDs deaths which corresponds to 31 million deaths in 2012.1 All these diseases involve a variation of H2S concentration in blood. Indeed, H2S is the 3rd endogenously generated gaseous signaling compound and it’s involved in the biological systems under physiological and pathological conditions.2 What about the development of accurate point-of-care testing3 for H2S blood concentration using fluorescent MOF as sensor? Early diagnostic will allow avoiding millions of deaths every year.2. Results and discussion We present a tailored MOF solid coupled for the first time with a femtosecond (fs)-pulse laser irradiation protocol to achieve the rapid in vitro detection of nanomolar sulfide in serum solutions.4 Three different MOF platforms are investigated here, namely MIL-68, MIL-101 and UiO-66. The detection is based on azido to amino turn on fluorescence upon H2S exposure (Fig. 1a).Our azido-modified Al-MIL-101 is thus an efficient sensor for sulfide in biologically relevant media, reaching the 100 nM detection limit under laser excitation (Fig. 1b). This result is a three order of magnitude sensitivity increase with respect to previously reported fluorescent azido-MOF which detected tens to hundreds micromolar sulfide under lamp excitation.5 The limit of determination of our system (100 nM) is also lower than that reported for the Ellman reagent (600 nM), which is widely used for the detection of SH-containing compounds produced by bacteria in solution. We assign the high sensitivity of our hybrid solid sys-tem to the arrangement of organic chromophore into the rigid MOF structure which allows sensing sites isolation and has proven to reduce non-radiative emissions. The latter are moreover efficiently neutralize by the highly energetic fs-pulse laser excitation leading to heightened ligand-centered emission.3. Conclusions In conclusion, the Al-MIL-101-based sensor allows reaching sulfide quantification in physiological solutions after only minutes of exposure in the micro- to nanomolar range for endogenous H2S concentrations. Through the adequate tuning of irradiation protocol, the rational selection of ligand-centered emission paves the way to MOF-based device construction by design, the hybrid solid capacity being driven by an almost infinite library of organic chromophore ligands.This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 685727References 1) Mendis, S.; Armstrong, T.; Bettcher, D.; Branca, F.; Lauer, J.; Mace, C.; Poznyak, V.; Riley, L.; Da Costa E Silva, V.; Steven, G. Global Status Report on noncommunicable diseases 2014, World Health Organization, 2015.2) Wang, R. Physiol. Rev. 2012, 92, 791.3) Luppa, P. B.; Müller, C.; Schlichtiger, A.; Schlebusch, H. TrAC-Trend Anal. Chem. 2011, 30, 887.4) Legrand, A.; Pastushenko, A.; Lysenko, V.; Geloen, A.; Quadrelli, E.A.; Canivet, J.; Farrusseng, D., Submitted5) (a) Zhang, X.; Zhang, J.; Hu, Q.; Cui, Y.; Yang, Y.; Qian, G. Appl. Surf. Sci. 2015, 355, 814. (b) Nagarkar, S. S.; Saha, T.; Desai, A. V.; Talukdar, P.; Ghosh, S. K. Sci. Rep. 2014, 4, 07053.

SSCI-VIDE+ING+JEC:FRM:DFA; International audience; Shape and size selectivity is a vital consideration for many industrial heterogeneous catalysts, which often lack the ability to convert specific molecules in a mixture of reactants, including catalyst poisons.Among MOFs, the zeolitic imidazolate frameworks (ZIFs), a sub-family constructed around imidazolate linkers,[1] show the high chemical stability required for applications in catalysis.Among ZIF representatives, the SIM-1, formulated as Zn(C10H10N4O2), is isostructural to ZIF-8 with sodalite structure and consists in Zn tetrahedra linked by carboxylimidazolate linkers. It presents a small pore diameter around 7.5 Å and narrow windows of ca. 5 Å.[2] The SIM-1 already demonstrated its wide versatility and efficiency for gas adsorption,[3] gas separation[4] and liquid phase heterogeneous catalysis.[5]Here we report the direct in situ SIM-1 film growth for the first time on platinum-loaded millimetric alumina beads (Figure 1).[6] In contrast to reported multistep growth of MOF layer on metal nanocrystals, we developed an easily scalable and widely applicable methodology to overlay catalytic objects with a MOF membrane. The supported SIM-1 layer is demonstrated to act as a molecular sieve when the SIM-1@Pt/Al2O3 beads are involved in Pt-catalyzed reactions.This hybrid material exhibits size-selective discrimination, as the hydrogenation of toluene could be totally suppressed, while ethylene conversion was hardly affected.The simple methodology reported here opens new perspectives in the design of shaped and highly selective hybrid core-shell catalytic solids.[1]a) R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. O'Keeffe, O. M. Yaghi, J. Am. Chem. Soc. 2009, 131, 3875; b) R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. O'Keeffe, O. M. Yaghi, Science 2008, 319, 939; c) K. S. Park, Z. Ni, A. P. Cote, J. Y. Choi, R. D. Huang, F. J. Uribe-Romo, H. K. Chae, M. O'Keeffe, O. M. Yaghi, Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 10186-10191.[2]M. Baias, A. Lesage, S. Aguado, J. Canivet, V. Moizan-Basle, N. Audebrand, D. Farrusseng, L. Emsley, Angew. Chem. Int. Ed. 2015, 54, 5971-5976.[3]H. Amrouche, S. Aguado, J. Pérez-Pellitero, C. Chizallet, F. Siperstein, D. Farrusseng, N. Bats, C. Nieto-Draghi, J. Phys. Chem. C 2011, 115, 16425-16432.[4]a) S. Aguado, J. Canivet, D. Farrusseng, J. Mater. Chem. 2011, 21, 7582-7588; b) S. Aguado, C. H. Nicolas, V. Moizan-Baslé, C. Nieto, H. Amrouche, N. Bats, N. Audebrand, D. Farrusseng, New J. Chem. 2011, 35, 41-44.[5]a) S. Aguado, J. Canivet, D. Farrusseng, Chem. Commun. 2010, 46, 7999-8001; b) S. Aguado, J. Canivet, Y. Schuurman, D. Farrusseng, J. Catal. 2011, 284, 207-214; c) J. Canivet, S. Aguado, C. Daniel, D. Farrusseng, ChemCatChem 2011, 3, 675-678.[6] Sonia Aguado, Sawsan El-Jamal, Frederic Meunier, Jerome Canivet and David Farrusseng, Submitted

SSCI-VIDE+ING+JEC:DFA; International audience; Metal-Organic-Frameworks appear to be appealing platforms for immobilization of single-site organometallic catalysts. The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Through post-synthetic ligand exchange methodology, we successfully proceeded to the heterogenization of this molecular catalyst via the synthesis of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and more selective for formate. Through the study of the behaviour of MOF systems having a controlled Rh loading, competitive catalytic reaction occurring inside the Cp*Rh@UiO-67 framework are postulated. Finally, a combined computational-experimetnal methodology allowed unravelling the band-gap as a new descriptor of the chemical compostion of the hybrid material, to assess ultimately the covalent incorporation of the organometallic catalyst within the framework.