Understanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited‐state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited‐state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance‐Raman, and transient‐absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)₂Ru^II(tpphz)Rh^ICp*] of [(tbbpy)₂Ru(tpphz)Rh(Cp*)Cl]Cl(PF₆)₂ (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD‐analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible‐light irradiation.

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 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 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.

A new dyad consisting of a Ru^II chromophore, a tetrapyridophenazine bridging ligand and a Rh(Cp*)Cl catalytic center, [Ru(tbbpy)₂(tpphz)Rh(Cp*)Cl]Cl(PF₆)₂, acts as durable photocatalyst for hydrogen production from water. Catalytic activity is observed for more than 650 hours. Electrochemical investigations reveal that up to two electrons can be transferred to the catalytic center by a thermodynamically favorable intramolecular process, which has so far not been reported for similar tpphz based supramolecular photocatalysts. Additionally, mercury poisoning tests indicate that the new dyad works as a homogeneous photocatalyst.

Cobaloximes are promising, earth‐abundant catalysts for the light‐driven hydrogen evolution reaction (HER). Typically, these cobalt(III) complexes are prepared in situ or employed in their neutral form, for example, [Co(dmgH)₂(py)Cl], even though related complex salts have been reported previously and could, in principle, offer improved catalytic activity as well as more efficient immobilization on solid support. Herein, we report an interdisciplinary investigation into complex salts [Co(dmgH)₂(py)₂]⁺[Co(dmgBPh₂)₂Cl₂]⁻, and [Co(dmgH)₂(py)₂]⁺BArF⁻. We describe their strategic syntheses from the commercially available complex [Co(dmgH)₂(py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light‐driven HER. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH)₂(py)₂]⁺[Co(dmgBPh₂)₂Cl₂]⁻, and [Co(dmgH)₂(py)Cl] on supported and free‐standing amino‐terminated ∼1‐nm‐thick carbon nanomembranes (CNMs). Photocatalytic H₂ evolution at such arrays was quantified with Pd microsensors by scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of “designer catalyst arrays”, nanoprinted in a desired pattern on a solid support.