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Breslow intermediates are very often elusive species whose application in frustrated Lewis pair (FLP) chemistry is unprecedented. Described herein is the use of a masked form of an O-borylated Breslow (OBB) intermediate that performs FLP-type activation of the carbonyl function of five different benzaldehyde derivatives with complete diastereoselectivity. The resulting compounds are characterised in solution by NMR spectroscopy (compounds 4-8) and in solid state by X-ray diffraction analysis (compounds 4-6). A combined kinetic and theoretical investigation reveals the associative nature of the rate determining step and suggests that the OBB intermediate part is never released during the whole process.
RESUMO
[Co(bapbpy)Cl]+ (bapbpy: 6,6'-bis(2-aminopyridyl)-2,2'-bipyridine) is a polypyridyl cobalt(II) complex bearing both a redox-active bipyridine ligand and pendant proton relays. This compound catalyzes electro-assisted H2 evolution in DMF with distinct mechanisms depending on the strength of the acid used as the proton source (pKa values ranging from 3.4 to 13.5 in DMF) and the applied potential. Electrochemical studies combining cyclic voltammetry and bulk electrolysis measurements enabled one to bring out four distinct catalytic processes. Where applicable, relevant kinetic information were obtained using either foot-of-the-wave analysis (FOWA) or analytical treatment of bulk electrolysis experiments. Among the different catalytic pathways identified in this study, a clear relationship between the catalyst performances and stability was evidenced. These results draw attention to a number of interesting considerations and may help in the development of future adequately designed catalysts.
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The design of molecular dyads combining a light-harvesting unit with an electroactive centre is highly demanded in the field of artificial photosynthesis. The versatile Copper-catalyzed Azide-Alkyne Cycloaddition (CuAAC) procedure was employed to assemble a ruthenium tris-diimine unit to an unprecedented azide-substituted copper diimine-dioxime moiety. The resulting RuIICuII dyad 4 was characterized by electrochemistry, 1H NMR, EPR, UV-visible absorption, steady-state fluorescence and transient absorption spectroscopies. Photoinduced electron transfer from the ruthenium to the copper centre upon light-activation in the presence of a sacrificial electron donor was established thanks to EPR-monitored photolysis experiments, opening interesting perspectives for photocatalytic applications.
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The coordination of the Lewis superacid tris(pentafluorophenyl)alane (AlCF) to phosphine-supported, group 6 bis(dinitrogen) complexes [ML2(N2)2] is explored, with M = Cr, Mo or W and L = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), dmpe (1,2-bis(dimethylphosphino)ethane) or 2 × PMe2Ph. Akin to tris(pentafluorophenyl)borane (BCF), AlCF can form 1 : 1 adducts by coordination to one distal nitrogen of general formula trans-[ML2(N2){(µ-η1:η1-N2)Al(C6F5)3}]. The boron and aluminium adducts are structurally similar, showing a comparable level of N2 push-pull activation. A notable exception is a bent (BCF adducts) vs. linear (AlCF adducts) M-N-N-LA motif (LA = Lewis acid), explained computationally as the result of steric repulsion. A striking difference arose when the formation of two-fold adducts was conducted. While in the case of BCF the 2 : 1 Lewis pairs could be observed in equilibrium with the 1 : 1 adduct and free borane but resisted isolation, AlCF forms robust 2 : 1 adducts trans-[ML2{(µ-η1:η1-N2)Al(C6F5)3}2] that isomerise into a more stable cis configuration. These compounds could be isolated and structurally characterized, and represent the first examples of trinuclear heterometallic complexes formed by Lewis acid-base interaction exhibiting p and d elements. Calculations also demonstrate that from the bare complex to the two-fold aluminium adduct, substantial decrease of the HOMO-LUMO gap is observed, and, unlike the trans adducts (1 : 1 and 1 : 2) for which the HOMO was computed to be a pure d orbital, the one of the cis-trinuclear compounds mixes a d orbital with a π* one of each N2 ligands. This may translate into a more favourable electrophilic attack on the N2 ligands instead of the metal centre, while a stabilized N2-centered LUMO should ease electron transfer, suggesting Lewis acids could be co-activators for electro-catalysed N2 reduction. Experimental UV-vis spectra for the tungsten family of compounds were compared with TD-DFT calculations (CAM-B3LYP/def2-TZVP), allowing to assign the low extinction bands found in the visible spectrum to unusual low-lying MLCT involving N2-centered orbitals. As significant red-shifts are observed upon LA coordination, this could have important implications for the development of visible light-driven nitrogen fixation.
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The production of hydrogen by efficient, low-cost, and integrated photoelectrochemical water splitting processes represents an important target for the ecological transition. This challenge can be addressed thanks to bioinspired chemistry and artificial photosynthesis approaches by designing dye-sensitized photocathodes for hydrogen production, incorporating bioinspired first-row transition metal-based catalysts. The present work describes the preparation and photoelectrochemical characterization of a NiO photocathode sensitized with a phosphonate-derivatized ruthenium tris-diimine photosensitizer covalently linked to a cobalt diimine dioxime hydrogen-evolving catalyst. Under simulated AM 1.5G irradiation, hydrogen is produced with photocurrent densities reaching 84 ± 7 µA·cm-2, which is among the highest values reported so far for dye-sensitized photocathodes with surface-immobilized catalysts. Thanks to the unique combination of advanced spectroscopy and surface characterization techniques, the fast desorption of the dyad from the NiO electrode and the low yield of electron transfer to the catalyst, resulting in the Co demetallation from the diimine dioxime framework, were identified as the main barriers limiting the performances and the stability of the system. This work therefore paves the way for a more rational design of molecular photocathodes for solar fuel production and represents a further step toward the development of sustainable processes for the production of hydrogen from sunlight and water.
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This work reports on the synthesis and characterization of a series of mononuclear thiosemicarbazone nickel complexes that display significant catalytic activity for hydrogen production in DMF using trifluoroacetic acid as the proton source. The ligand framework was chemically modified by varying the electron-donating abilities of the para substituents on the phenyl rings, which was expected to impact the capability of the resulting complexes to reduce protons into hydrogen. Over the four nickel complexes that were obtained, the one with the thiomethyl substituent, NiSCH3, was found to overtake the catalytic performances of the parent complex NiOCH3 featuring lower overpotential values and similar maximum turnover frequencies. These results confirm the electronic effects of the ligand on HER when using thiosemicarbazone nickel complexes and support that chemical modifications can tune the catalytic performances of such systems.
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The ability of [RuII(tButpy)(dmbpy)(MeCN)]2+ (1-MeCN) to capture CO2, with the assistance of triethanolamine (TEOA), has been assessed under photocatalytically-relevant conditions. The photolability of 1-MeCN has proven essential to generate a series of intermediates which only differ by the nature of their monodentate ligand. In DMF, ligand photoexchange of 1-MeCN to give [RuII(tButpy)(dmbpy)(DMF)]2+ (1-DMF) proceeds smoothly with a quantum yield of 0.011. However, in the presence of TEOA, this process was disrupted, leading to the formation of a mixture of 1-DMF and [RuII(tButpy)(dmbpy)(TEOA)]+ (1-TEOA). An equilibrium constant of 3 was determined. Interestingly, 1-TEOA demonstrated an ability to reversibly catch and release CO2 making it a potentially crucial intermediate towards CO2 reduction.
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The human genome is replete with repetitive DNA sequences that can fold into thermodynamically stable secondary structures such as hairpins and quadruplexes. Cellular enzymes exist to cope with these structures whose stable accumulation would result in DNA damage through interference with DNA transactions such as transcription and replication. Therefore, the chemical stabilization of secondary DNA structures offers an attractive way to foster DNA transaction-associated damages to trigger cell death in proliferating cancer cells. While much emphasis has been recently given to DNA quadruplexes, we focused here on three-way DNA junctions (TWJ) and report on a strategy to identify TWJ-targeting agents through a combination of in vitro techniques (TWJ-screen, polyacrylamide gel electrophoresis, fluorescence resonance energy transfer-melting, electrospray ionization mass spectrometry, dialysis equilibrium, and sulforhodamine B assays). We designed a complete workflow and screened 1200 compounds to identify promising TWJ ligands selected on stringent criteria in terms of TWJ-folding ability, affinity, and selectivity.
Assuntos
DNA/metabolismo , Bibliotecas de Moléculas Pequenas/metabolismo , Antineoplásicos/metabolismo , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , DNA/genética , Eletroforese em Gel de Poliacrilamida , Transferência Ressonante de Energia de Fluorescência , Humanos , Ligantes , Conformação de Ácido Nucleico , Bibliotecas de Moléculas Pequenas/farmacologia , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
Understanding the structural and electronic factors governing the efficiency of dye-sensitized NiO photocathodes is essential to optimize solar fuel production in photoelectrochemical cells (PECs). For these purpose, three different ruthenium dyes, bearing either two or four methylphosphonate anchoring groups and either a bipyridine or a dipyridophenazine ancillary ligand, were synthesized and grafted onto NiO films. These photoelectrodes were fully characterized by XPS, ToF-SIMS, UV-vis absorption, time-resolved emission and femtosecond transient absorption spectroscopies. Increasing the number of anchoring groups from two to four proved beneficial for the grafting efficiency. No significant modification of the electronic properties compared to the parent photosensitizer was observed, in accordance with the non-conjugated nature of the grafted linker. The photoelectrochemical activity of the dye-sensitized NiO electrodes was assessed in fully aqueous medium in the presence of an irreversible electron acceptor and photocurrents reaching 190 µA.cm-2 were recorded. The transient absorption study revealed the presence of two charge recombination pathways for each of the sensitizers and evidenced a stabilized charge separated state in the dppz derivative, supporting its superior photoelectrochemical activity.
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Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second-order rate constant of 2.5 × 104â M-1â s-1; turnover frequency of 250â s-1 at 10â mM H+ concentration) from mildly acidic solutions.
Assuntos
Materiais Biomiméticos/química , Complexos de Coordenação/química , Hidrogênio/química , Hidrogenase/química , Níquel/química , Materiais Biomiméticos/síntese química , Materiais Biomiméticos/metabolismo , Catálise , Domínio Catalítico , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Hidrogenase/metabolismo , Modelos Moleculares , Conformação Molecular , Oxirredução , PrótonsRESUMO
Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push-pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.
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We describe a method to induce by light a reversible switch from a continuous two-phase laminar flow to a droplet generating regime, in microfluidic devices with a usual water-in-oil flow focusing geometry. It consists in adding a photosensitive surfactant to the aqueous phase to modulate using light the interfacial energy between flowing liquids and the microfluidic substrate. We show that UV irradiation induces liquid fragmentation into monodisperse water microdroplets and that many cycles of reversible and rapid switches (<2 s) between continuous laminar flows and stable droplet regimes can be realized. By spatially controlling the application of the light stimulus, we also demonstrate the first spatially resolved remote induction of droplet generation.