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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

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) 2 Ru-BL-Rh(Cp*)Cl] 3+ photocatalysts just differing in the central part (alkynyl, triazole or phenazine) of the bridging ligand (BL) we were 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 III center but rather the rate at which a two-fold reduced Rh I species is generated can directly be correlated with the observed photocatalytic formation of NADH from NAD + . Interestingly, the complex which exhibited the fastest intramolecular electron transfer kinetics for the first electron is not the one that allowed the fastest photocatalysis. With the photocatalytically most efficient alkynyl linked system, it was even possible to overcome the rate of thermal NADH formation. Moreover, for this photocatalyst loss of the alkynyl functionality under photocatalytic conditions was identified as an important deactivation pathway.

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. To show the concept we combine electrical impedance spectroscopy with steady state spectroscopy. As light-driven hole injection from Os complex to the PPV polymer is thermodynamically feasible both based on reductive quenching of photoexcited PPV and based on oxidative quenching of the photoexcited Os chromophores we investigate the impact of illumination wavelengths on the photocathode behavior and photochemical stability of the material. While both blue and red light excitation, i.e., excitation of the chromophoric units PPV and excitation of the metal-to-ligand charge transfer transitions in the side-chain pendant Os chromophores yield cathodic photocurrents, the photochemical stability is drastically enhanced upon red-light excitation. Hence, the results of the investigations discussed show the validity of the concept developing red-light sensitized hole-conducting polymers for energy conversion.

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)2Ru-BL-Rh(Cp*)Cl]3+ 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 RhIII center but rather the rate at which a two-fold reduced RhI species is generated can directly be correlated with the observed photocatalytic formation of NADH from NAD+. Interestingly, the complex which exhibits the fastest intramolecular electron transfer kinetics for the first electron is not the one that allows the fastest photocatalysis. With the photocatalytically most efficient alkynyl linked system, it is even possible to overcome the rate of thermal NADH formation by avoiding the rate-determining β-hydride elimination step. Moreover, for this photocatalyst loss of the alkynyl functionality under photocatalytic conditions is identified as an important deactivation pathway.

Originally planned as an on-site meeting, the inaugural CataLight Young Scientist Symposium (CYSS) took place as a fully online conference in November 2020. Dedicated to various aspects of photocatalysis, namely synthesis, theory, characterization, and application, CYSS aimed to provide a stage for early-career scientists to connect to each other and present their research to peers in the field. While still keeping a traditional on-site conference format including both plenary and poster sessions, several minor and major changes had to be applied to the format to deliver a full experience. In this report, we highlight key steps in the organization of such an online conference, laying a focus on using mostly open source software to minimize costs, and discuss differences to both on-site and other online conference formats.

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. Above the upper limit of concentration (a lower micromolar range for the present class of compounds), experimental data delivered conflicting results and the concentration should not therefore be exceeded. Scanning force microscopy and molecular dynamics simulations confirm the formation of one-dimensional aggregates with presumably helical arrangement of the achiral monomers.