Unexpected Redox Chemistry of P∩N- and As∩N-Rhenium(I) Tricarbonyl Complexes in the Presence of CO2 Acting as an Acid.

This study reports on Re tricarbonyl complexes bearing 8-(diphenylphosphanyl)quinoline, P∩N, and 8-(diphenylarsanyl)quinoline, As∩N, as bidendate ligands. We studied the reactivity of these complexes in comparison with fac-Re(N∩N)(CO)3Cl (with N∩N = 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine). We used a combination of electrochemical and spectroelectrochemical methods with time-resolved spectroscopy over 10 orders of magnitude (100 ps-1 s) to investigate the peculiar reactivity of one-electron-reduced Re(CO)3(P∩N)Cl and Re(CO)3(As∩N)Cl complexes also in the presence of protons.

Flexible to rigid: IR spectroscopic investigation of a rhenium-tricarbonyl-complex at a buried interface.

This work explores the solid-liquid interface of a rhenium-tricarbonyl complex embedded in a layer of zirconium oxide deposited by atomic layer deposition (ALD). Time-resolved and steady state infrared spectroscopy were applied to reveal the correlations between the thickness of the ALD layer and the spectroscopic response of the system. We observed a transition of the molecular environment from flexible to rigid, as well as limitations to ligand exchange and excited state quenching on the embedded complexes, when the ALD layer is roughly of the same height as the molecules.

About Control: Kinetics in Molecule- based Photochemical Water Reduction Investigated by Transient IR Spectroscopy.

This review aims to promote the role of transient IR spectroscopy to investigate molecular-based photocatalytic water reduction. Examples are discussed in which this method has been successfully applied to elucidate reaction mechanisms. Focus is given to kinetic changes and their consequences when a photochemical water reduction system, which is functional and well understood in solution, is brought onto a metal oxide surface.

Nanosecond protein dynamics in a red/green cyanobacteriochrome revealed by transient IR spectroscopy.

Over the last decades, photoreceptive proteins were extensively studied with biophysical methods to gain a fundamental understanding of their working mechanisms and further guide the development of optogenetic tools. Time-resolved infrared (IR) spectroscopy is one of the key methods to access their functional non-equilibrium processes with high temporal resolution but has the major drawback that experimental data are usually highly complex. Linking the spectral response to specific molecular events is a major obstacle. Here, we investigate a cyanobacteriochrome photoreceptor with a combined approach of transient absorption spectroscopy in the visible and IR spectral regions. We obtain kinetic information in both spectral regions by analysis with two different fitting methods: global multiexponential fitting and lifetime analysis. We investigate the ground state dynamics that follow photoexcitation in both directions of the bi-stable photocycle (Pr* and Pg*) in the nanosecond and microsecond time regimes. We find two ground state intermediates associated with the decay of Pr* and four with Pg* and report the macroscopic time constants of their interconversions. One of these processes is assigned to a structural change in the protein backbone.

Rhodium-coordinated poly(arylene-ethynylene)-alt-poly(arylene-vinylene) copolymer acting as photocatalyst for visible-light-powered NAD⁺/NADH reduction.

A 2,2'-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD(+)/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390-650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD(+). With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled.

Photocatalytic reduction of artificial and natural nucleotide co-factors with a chlorophyll-like tin-dihydroporphyrin sensitizer.

An efficient photocatalytic two-electron reduction and protonation of nicotine amide adenine dinucleotide (NAD(+)), as well as the synthetic nucleotide co-factor analogue N-benzyl-3-carbamoyl-pyridinium (BNAD(+)), powered by photons in the long-wavelength region of visible light (λirr > 610 nm), is demonstrated for the first time. This functional artificial photosynthetic counterpart of the complete energy-trapping and solar-to-fuel conversion primary processes occurring in natural photosystem I (PS I) is achieved with a robust water-soluble tin(IV) complex of meso-tetrakis(N-methylpyridinium)-chlorin acting as the light-harvesting sensitizer (threshold wavelength of λthr = 660 nm). In buffered aqueous solution, this chlorophyll-like compound photocatalytically recycles a rhodium hydride complex of the type [Cp*Rh(bpy)H](+), which is able to mediate regioselective hydride transfer processes. Different one- and two-electron donors are tested for the reductive quenching of the irradiated tin complex to initiate the secondary dark reactions leading to nucleotide co-factor reduction. Very promising conversion efficiencies, quantum yields, and excellent photosensitizer stabilities are observed. As an example of a catalytic dark reaction utilizing the reduction equivalents of accumulated NADH, an enzymatic process for the selective transformation of aldehydes with alcohol dehydrogenase (ADH) coupled to the primary photoreactions of the system is also demonstrated. A tentative reaction mechanism for the transfer of two electrons and one proton from the reductively quenched tin chlorin sensitizer to the rhodium co-catalyst, acting as a reversible hydride carrier, is proposed.

Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode.

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g-1. This is on par with the best solution-phase amine chemical capture technologies available today.

Characterization of a non-aggregating silicon(IV) phthalocyanine in aqueous solution: toward red-light-driven photocatalysis based on earth-abundant materials.

Photophysical and photochemical characterization of a novel cationic silicon phthalocyanine with excellent water solubility properties is reported. The robust red-light responsive compound shows very attractive features as a sensitizer for reductive and oxidative quenching processes to trigger photocatalytic substrate conversion in aqueous solution.