The photoredox activity of well-known Ru II complexes stems from metal-to-ligand charge transfer (MLCT) excited states, in which a ligand-based electron can initiate chemical reductions and a metal-centered hole can trigger oxidations. Cr III polypyridines show similar photoredox properties, although they have fundamentally different electronic structures. Their photoactive excited state is of spin-flip nature, differing from the electronic ground state merely by a change of one electron spin, but with otherwise identical d-orbital occupancy. We find that the driving-force dependence for photoinduced electron transfer from 10 different donors to a spin-flip excited state of a Cr III complex is very similar to that for a Ru II polypyridine, and thereby validate the concept of estimating the redox potential of d 3 spin-flip excited states in analogous manner as for the MLCT states of d 6 compounds. Building on this insight, we use our Cr III complex for photocatalytic reactions not previously explored with this compound class, including the aerobic bromination of methoxyaryls, oxygenation of 1,1,2,2-tetraphenylethylene, aerobic hydroxylation of arylboronic acids, and the vinylation of N -phenyl pyrrolidine. This work contributes to understanding the fundamental photochemical properties of first-row transition-metal complexes in comparison to well-explored precious-metal-based photocatalysts.

The formation of so-called solar fuels from abundant low-energetic compounds, such as carbon dioxide or water, relies on the chemical elementary steps of photoinduced electron transfer and accumulation of multiple redox equivalents. The majority of molecular systems explored to date require sacrificial electron donors to accumulate multiple electrons on a single acceptor unit, but the use of high-energetic sacrificial redox reagents is unsustainable. In recent years, an increasing number of molecular compounds for reversible light-driven accumulation of redox equivalents that do not need sacrificial electron donors has been reported. Those compounds are the focus of this mini review. Different concepts, such as redox potential compression (achieved by proton-coupled electron transfer, Lewis acid–base interactions, or structural rearrangements), hybrids with inorganic nanoparticles, and diffusion-controlled multi-component systems, will be discussed. Newly developed strategies to outcompete unproductive reaction pathways in favor of desired photoproduct formation will be compared, and the importance of identifying reaction intermediates in the course of multiphotonic excitation by different time-resolved spectroscopic techniques will be discussed. The mechanistic insights gained from molecular donor–photosensitizer–acceptor compounds inform the design of next-generation charge accumulation systems for solar energy conversion.

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Numerous studies have explored the kinetics of light-induced charge separation and thermal charge recombination in donor–acceptor compounds, but quantum efficiencies have rarely been investigated. Here, we report on two essentially isomeric molecular triads, both comprising a π-extended tetrathiafulvalene (ExTTF) donor, a ruthenium­(II)-based photosensitizer, and a naphthalene diimide (NDI) acceptor. The key difference between the two triads is how the NDI acceptor is connected. Linkage at the NDI core provides stronger electronic coupling to the other molecular components than connection via the nitrogen atoms of NDI. This change in molecular connectivity is expected to accelerate both energy-storing charge separation and energy-wasting charge recombination processes, but it is not a priori clear how this will affect the triad’s ability to store photochemical energy; any gain resulting from faster charge separation could potentially be (over)­compensated by losses through accelerated charge recombination. The new key insight emerging from our study is that the quantum yield for the formation of a long-lived charge-separated state increases by a factor of 5 when going from nitrogen- to core-connected NDI, providing the important proof of concept that better molecular connectivity indeed enables more efficient photochemical energy storage. The physical origin of this behavior seems to root in different orbital connectivity pathways for charge separation and charge recombination, as well as in differences in the relevant orbital interactions depending on NDI connection. Our work provides guidelines for how to discriminate between energy-storing and energy-wasting electron transfer reactions in order to improve the quantum yields for photochemical energy storage and solar energy conversion.