Outpacing conventional nicotinamide hydrogenation catalysis by a strongly communicating heterodinuclear photocatalyst.

Unequivocal assignment of rate-limiting steps in supramolecular photocatalysts is of utmost importance to rationally optimize photocatalytic activity. By spectroscopic and catalytic analysis of a series of three structurally similar [(tbbpy)Ru-BL-Rh(Cp*)Cl] photocatalysts just differing in the central part (alkynyl, triazole or phenazine) of the bridging ligand (BL) we are able to derive design strategies for improved photocatalytic activity of this class of compounds (tbbpy = 4,4´-tert-butyl-2,2´-bipyridine, Cp* = pentamethylcyclopentadienyl). Most importantly, not the rate of the transfer of the first electron towards the Rh center but rather the rate at which a two-fold reduced Rh species is generated can directly be correlated with the observed photocatalytic formation of NADH from NAD.

Influence of the Linker Chemistry on the Photoinduced Charge-Transfer Dynamics of Hetero-dinuclear Photocatalysts.

To optimize light-driven catalytic processes, light-mediated multi-electron transfer dynamics in molecular dyads need to be studied and correlated with structural changes focusing on the catalytically active metastable intermediates. Here, spectro-electrochemistry has been employed to investigate the structure-dependent photoelectron transfer kinetics in catalytically active intermediates of two Ru-Rh catalysts for light-driven NAD reduction. The excited-state reactivity of short-lived intermediates was studied along different photoreaction pathways by resonance Raman and time-resolved transient absorption spectro-electrochemistry with sub-picosecond time resolution under operando conditions.

Red-light sensitized hole-conducting polymer for energy conversion.

We report a novel hole conductive polymer with photoactive Os(ii) complexes in the side chains. This PPV derivative can be activated upon absorption of red visible light and delivers notable photocurrents when used as photocathode material. Thus, the polymer presents as a stepping stone towards developing soft matter alternatives to NiO photocathodes, which function under visible light irradiation.

Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers.

A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with Ru complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode-electrolyte interface was examined with chopped-light chronoamperometry.

Supramolecular polymerization: challenges and advantages of various methods in assessing the aggregation mechanism.

Oligothiophenes with branched alkyl end groups show distinct aggregation in organic solvents. The process of supramolecular polymerization is assessed by three different methods (UV-vis absorption and fluorescence emission spectroscopy and dynamic light scattering) to exclude artifacts. An apparent dependence of the degree of aggregation on the concentration of the oligomers is observed.