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Graph measures represent an optimal way to investigate neural networks’ organization, yet their application is still limited in developmental samples. To uncover the organization of 7-month-old infants’ functional brain networks during an emotional perception task, we combined a decoding technique (i.e., Principal Component Regression) to graph metrics computation. Nodes’ Within Module Degree Z Score (WMDZ) was computed as a measure of modular organization, and we decoded networks’ functional organizations across EEG alpha and theta bands in response to static and dynamic facial expressions of emotions. We found that infants’ brain topological activity differentiates between static and dynamic emotional faces due to the involvement of visual streams and sensorimotor areas, as often observed in adults. Moreover, network invariances point toward an already present rudimental network structure tuned to face processing already at 7-months of age. Overall, our results affirm the fruitfulness of the application of graph measures in developmental samples, due to their flexibility and the wealth of information they provide over infants’ networks functional organization.

Atomic Layer Deposition (ALD) is a gas-phase deposition technique based on sequential, self-limiting surface reactions which appears well-adapted to obtain conformal film growth with precise thickness level control, good reproducibility and homogeneity over nanostructured supports.[1] This property is relevant for example, for the functionalization of nanostructured supports useful for energy conversion devices.[1]In this talk we will show the use of surface organometallic chemistry to discover and transfer to industrially relevant substrates novel ALD Processes for the growth of targeted phases. Examples will be given on MoS2, [2] Al2O3@BiVO4 [3], TiS2[4] and the porous metal organic framework ZIF-8[5]. ______________References: [1] J. Bachmann, Beilstein J. Nanotechnol. 2014, 5, 245–248[2] Cadot, S; Renault, O. ; Fregnaux, M.; Rouchon, D.; Nolot, E.; Szeto, K.; Thieuleux, C.; Veyre, L.; Okuno, H. ; Martin, F*. et Quadrelli , E. A.* Nanoscale, 9 , 538-546 (2017). DOIhttps://doi.org/10.1039/C6NR06021H[3] 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) https://doi.org/10.1016/j.apcata.2020.117796 .......[4] “Transition Metal Dichalcogenide TiS2 prepared by Molecular Layer Deposition and thermal annealing: atomic-level insights with In situ X-ray studies and molecular surface chemistry”. P. Abi Younes,*, E. V. Skopin, M. Zhukush, N. Gauthier, L. Rapenne, H. Roussel, N. Aubert, L. Khrouz, C. Camp, M. I. Richard, N. Schneider, G. Ciatto, D. Rouchon, E. A. Quadrelli,* and H. Renevier,* , in preparation [5] V. Perrot, A. Roussey, F. Ricoul, A. Benayad, M. Veillerot. A. Sole-Daura, J. Canivet, C. mellot-Draznieks, Elsje A. Quadrelli,* Vincent Jousseaume*, in preparation

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.

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

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Completely vapor phase-based routes for the synthesis of Metal Organic Frameworks (MOF) are recent (see, for example, [1] and [2]).Vapour-phase processes are usually preferred to obtain conformal coatings in the high aspect ratio features of devices but much still remains to be done to control the growth and understand the potential and the limits of these growth methods.In this work, pinhole-free and crystalline zeolitic imidazolate framework-8 (ZIF-8) layers as thick as 250 nm were grown, by integrating the method previously reported [1]- which typically levels off below 100 nm- in a novel cycling process.Different types of substrates and devices were used, such as silicon wafers, Quartz Crystal Microbalance and silicon micro-pillars arrays, see Figure1).The material properties as well as the impact of the process parameters on the MOF growth will be reported (data include electronic microscopy, ellipsometric-porosimetry, X-ray diffraction and a study on the influence of water pressure on the final thickness).Molecular-level mechanistic reasons behind the current thickness bottleneck will be discussed through a ToF-SIMS and XPS profil study at different stages of growth.[1] I. Stassen et al., Nat. Mat., 15, 304–310 (2016)[2] E. Ahvenniemi et al., Chem. Com., 52, 1139-1142 (2016)

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: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+EQD; International audience; None

One of the most important aspects of social interactions concerns the ability to discern social signals conveyed by other people. We know that adults and pre-schoolers easily distinguish between fine-grained differences in the level of trustworthiness expressed by faces. Nevertheless, only a few studies investigated the sensitivity to social signals of trustworthiness in infancy (Jessen & Grossmann, 2016; Jessen & Grossmann, 2017). By using computer-generated faces of male identities, these studies found no evidence of neural discrimination between trustworthy and untrustworthy faces, although both face types were discriminated from neutral faces. In this study, we aimed at investigating whether, at the age of 6 months, infants are able to discern between trustworthy and untrustworthy faces of truthful female identities. Infants were administered with a Fast-Periodic Visual Stimulation (FPVS) task, where two face identities were presented at a rate of 6 Hz (Baseline) following an Oddball paradigm. Every 1.2 Hz (Oddball), the trustworthiness level changed (a trustworthy face every 4 untrustworthy faces, or vice versa, in a counterbalanced order). Preliminary analyses show significant Signal-to-Noise Ratios (SNRs) at 6 Hz in occipital regions. More importantly, significant SNRs at 1.2 Hz were found in right occipital and right occipito-temporal regions. These results suggest that at 6 months infants are able to discriminate between different levels of trustworthiness, and that this discrimination takes place in brain areas known to play an important role in face discrimination. Future studies should investigate how fine-grained this sensitivity is, and how brain sensitivity is related to behavioural responses.