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131.
Fakourou Camara Thomas Gavaggio Baptiste Dautreppe Jrme Chauvin Jacques Pcaut Dmitry Aldakov Marie-Noëlle Collomb Jrme Fortage 《Molecules (Basel, Switzerland)》2022,27(19)
Molecular hydrogen (H2) is considered one of the most promising fuels to decarbonize the industrial and transportation sectors, and its photocatalytic production from molecular catalysts is a research field that is still abounding. The search for new molecular catalysts for H2 production with simple and easily synthesized ligands is still ongoing, and the terpyridine ligand with its particular electronic and coordination properties, is a good candidate to design new catalysts meeting these requirements. Herein, we have isolated the new mono-terpyridyl rhodium complex, [RhIII(tpy)(CH3CN)Cl2](CF3SO3) (Rh-tpy), and shown that it can act as a catalyst for the light-induced proton reduction into H2 in water in the presence of the [Ru(bpy)3]Cl2 (Ru) photosensitizer and ascorbate as sacrificial electron donor. Under photocatalytic conditions, in acetate buffer at pH 4.5 with 0.1 M of ascorbate and 530 μM of Ru, the Rh-tpy catalyst produces H2 with turnover number versus catalyst (TONCat*) of 300 at a Rh concentration of 10 μM, and up to 1000 at a concentration of 1 μM. The photocatalytic performance of Ru/Rh-tpy/HA–/H2A has been also compared with that obtained with the bis-dimethyl-bipyridyl complex [RhIII(dmbpy)2Cl2]+ (Rh2) as a catalyst in the same experimental conditions. The investigation of the electrochemical properties of Rh-tpy in DMF solvent reveals that the two-electrons reduced state of the complex, the square-planar [RhI(tpy)Cl] (RhI-tpy), is quantitatively electrogenerated by bulk electrolysis. This complex is stable for hours under an inert atmosphere owing to the π-acceptor property of the terpyridine ligand that stabilizes the low oxidation states of the rhodium, making this catalyst less prone to degrade during photocatalysis. The π-acceptor property of terpyridine also confers to the Rh-tpy catalyst a moderately negative reduction potential (Epc(RhIII/RhI) = −0.83 V vs. SCE in DMF), making possible its reduction by the reduced state of Ru, [RuII(bpy)(bpy•−)]+ (Ru−) (E1/2(RuII/Ru−) = −1.50 V vs. SCE) generated by a reductive quenching of the Ru excited state (*Ru) by ascorbate during photocatalysis. A Stern–Volmer plot and transient absorption spectroscopy confirmed that the first step of the photocatalytic process is the reductive quenching of *Ru by ascorbate. The resulting reduced Ru species (Ru−) were then able to activate the RhIII-tpy H2-evolving catalyst by reduction generating RhI-tpy, which can react with a proton on a sub-nanosecond time scale to form a RhIII(H)-tpy hydride, the key intermediate for H2 evolution. 相似文献
132.
Mariem Ghali Chaima Brahmi Mahmoud Benltifa Cyril Vaulot Aissam Airoudj Philippe Fioux Frédéric Dumur Corine Simonnet-Jégat Fabrice Morlet-Savary Salah Jellali Latifa Bousselmi Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2021,59(2):153-169
Different inorganic/organic photocomposites based on polyoxometalate (POM) nanoparticles have been developed for photocatalytic applications. Currently, polyoxometalate nanoparticles have been successfully in-situ embedded into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The proposed POM/polymer photocomposites have been characterized using complementary techniques for a better understanding of their photocatalytic activity. Interestingly, the obtained photocomposites exhibit high rigidity, excellent thermal stability, a non-negligible porosity and new functionalities such as light reactivity and redox properties. Moreover, developed composites showed efficient catalytic activity for the color removal of aqueous solutions of erythrosine and rose Bengal under Light Emitting Diodes LED@375 nm irradiation reaching 80 and 90% as a final color removal, respectively. 相似文献
133.
Dolorès Edmont Yvon Buisson Philippe Treillard Christophe Plisson Jacques Chenault 《合成通讯》2013,43(2):217-225
A high yielding N-amination of quinolones at low temperature via the use of O-mesitylenesulfonylhydroxylamine is reported. 相似文献
134.
Jacques Le Moigne Armand Soldera Daniel Guillon Antoine Skoulios 《Liquid crystals》2013,40(6):627-639
Abstract Acetylenic and diacetylenic mesomorphic monomers have been prepared in order to obtain long conjugated polymers able to give high non-linear optical hyperpolarizabilities. Here we report the synthesis of such monomers incorporating cholesteryl and methoxybiphenyl groups; their structural and thermal behaviour are described. The occurrence of mesophases in the acetylenic and diacetylenic derivatives is discussed as a function of the spacer length and of the size of the mesogen moiety. The diacetylenic derivatives containing the methoxybiphenyl groups do not exhibit any liquid-crystalline behaviour but are able to polymerize under U.V. radiation. 相似文献
135.
The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases. 相似文献
136.
Tharwat Mohy El Dine David Evans Prof. Jacques Rouden Dr. Jérôme Blanchet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5894-5898
A highly efficient and mild transamidation of amides with amines co‐catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α‐amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron‐derived Lewis acidity rather than an improved Brønsted acidity of acetic acid. 相似文献
137.
Bis(trimethylsilyl) peroxide can be readily obtained by reaction of trimethylchlorosilane with the hexamethylenetetramine-hydrogene peroxide complex. 相似文献
138.
139.
140.
Alexandra Botz Yves Chenavier Jacques Pécaut Pascale Delangle Christelle Gateau 《Tetrahedron letters》2018,59(26):2550-2553
The synthesis of several thiazonaphthalimide derivatives is described. The exclusive formation of angular rather than linear isomers was unequivocally demonstrated by NMR and single crystal X-ray diffraction. Their photophysical properties and ability to bind calf-Thymus DNA with affinities in the range of 104 makes them interesting candidates to probe DNA by fluorescence. 相似文献