Christopher B. Larsen

Ruthenium(II) polypyridyl complexes exhibit rich excited state reactivity from both photogenerated 3MLCT and higher energy thermally populated ligand-field (LF) excited states. In order to maximize the utility of the different reactivity of these two states, the energy gap between them must be tuned without sacrificing the favorable optical and photophysical properties of the complex. In probing design strategies aimed at enhancing the photostability of RuII complexes for nondissociative photochemical applications, we herein explore the use of Chugaev-type dicarbene ligands as strong σ-donors. Using a complementary combination of X-ray crystallography, electrochemistry, and optical and X-ray spectroscopies, we demonstrate how Chugaev-type dicarbene ligands destabilize LF states of photoactive RuII complexes without sacrificing the favorable optical and photophysical properties of the complex, and compare with π-accepting methylisocyanide ligands. Despite these design strategies aimed at suppressing dissociative excited-state ligand-field pathways, we further report an unexpected dechelative photoelimination of hydrazine from the RuII Chugaev-type dicarbene complexes that occurs directly from the 3MLCT excited state with quantum yields in the order of ca. 1–5%, and is sensitive to peripheral substitution of chromophoric bipyridine ligands. These findings contribute to growing understanding of molecular design principles for photoactive RuII complexes targeted at either dissociative/nondissociative photochemical applications and introduce a new potential scaffold and photorelease mechanism for photoactivated chemotherapy.

Proton-coupled electron transfer (PCET) is foundational to catalysis, bioenergetics, and energy conversion, yet directly observing the interplay between electronic redistribution, protonation, and solvent reorganization remains challenging. We combine femtosecond optical spectroscopy, ultrafast N K-edge X-ray absorption spectroscopy, and time-resolved X-ray solution scattering to capture the steps of a sequential PCET reaction in water with atomic-site specificity. Using a ruthenium polypyridyl model complex, we resolve the electron redistribution upon photoinduced metal-to-ligand charge transfer and subsequent ( ~ 460 ps) protonation at a ligand nitrogen, as well as the concomitant rearrangement of the first-solvation-shell. Combined with advanced electronic structure and molecular dynamics simulations, our measurements reveal a marked localization of the excited-state electron density at the protonated N site, together with a switch from N···HO to NH···O hydrogen-bonds. These results establish a multimodal X-ray framework for mechanistic insight into PCET and its control in catalysis, artificial photosynthesis, and biological energy flow.

“A beaker, in a beaker, in a bucket” – a tuneable photoreactor system that can be rapidly assembled from readily available components is detailed. Involving interchangeable reaction coils and LED light sources, the system is designed to be accessible and affordable, allowing chemists to employ the well documented benefits of (flow) photochemistry to obtain proof-of-concept, without requiring investment in commercial equipment or in house fabrication of components. The flow photoreactor system, which can also be employed for batch reactions, has been characterised, and the visible light (460 nm) isomerisation of trans - to cis -stilbene, employing Ir(ppy) ₃ as a photosensitiser, has been used as a model reaction to evaluate its performance. It was found that the photostationary state of this reaction could be achieved within just 2 min of irradiation in flow with a 20 mW cm ^− 2 light source, allowing for reactor throughputs as high as 0.5 mmol min ^− 1 , demonstrating the utility of this easy to access system.

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal-ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. We investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here, [Ni(mpo)₂] (mpo = 2-mercaptopyridine-N-oxide) provides a representative example for the larger chemical class and is an active electro- and photocatalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo)₂] is presented based on ultrafast transient X-ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo)₂]^-) and relaxation to a pseudotetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands, and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal-ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt)₂]^n- and [Ni(mnt)₂]^n- anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core-valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal-ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal "ligand field" or "d-d" states that typically dominate the photophysics of 3d metal complexes but with significant metal-ligand charge transfer character dictated by their covalency. These results suggest that strong metal-ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.

The protonation of several Ni-centered pyridine-2-thiolate photocatalysts for hydrogen evolution is investigated using X-ray absorption spectroscopy (XAS). While protonation of the pyridinethiolate ligand was previously thought to result in partial dechelation from the metal at the pyridyl N site, we instead observe complete dissociation of the protonated ligand and replacement by solvent molecules. A combination of Ni K-edge and S K-edge XAS of the catalyst Ni(bpy)(pyS)₂ (bpy = 2,2'-bipyridine; pyS = pyridine-2-thiolate) identifies the structure of the fully protonated catalyst as a solvated [Ni(bpy)(DMF)₄]²⁺ (DMF = dimethylformamide) complex and the dissociated ligands as the N-protonated 2-thiopyridone (pyS-H). This surprising result is further supported by UV-vis absorption spectroscopy and DFT calculations and is demonstrated for additional catalyst structures and solvent environments using a combination of XAS and UV-vis spectroscopy. Following protonation, electrochemical measurements indicate that the solvated Ni bipyridine complex acts as the primary electron-accepting species during photocatalysis, resulting in separate protonated ligand and reduced Ni species. The role of ligand dissociation is considered in the larger context of the hydrogen evolution reaction (HER) mechanism. As neither the pyS-H ligand nor the Ni bipyridine complex acts as an efficient HER catalyst alone, the critical role of ligand coordination is highlighted. This suggests that shifting the equilibrium toward bound species by addition of excess protonated ligand (2-thiopyridone) may improve the performance of pyridinethiolate-containing catalysts.

The ability to access panchromatic absorption and long-lived charge-transfer (CT) excited states is critical to the pursuit of abundant-metal molecular photosensitizers. Fe(II) complexes supported by benzannulated diarylamido ligands have been reported to broadly absorb visible light with nanosecond CT excited state lifetimes, but as amido donors exert a weak ligand field, this defies conventional photosensitizer design principles. Here, we report an aerobically stable Fe(II) complex of a phenanthridine/quinoline diarylamido ligand, Fe(^ClL)₂, with panchromatic absorption and a 3 ns excited-state lifetime. Using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L-edge and N K-edge, we experimentally validate the strong Fe–N_amido orbital mixing in Fe(^ClL)₂ responsible for the panchromatic absorption and demonstrate a previously unreported competition between ligand-field strength and metal–ligand (Fe–N_amido) covalency that stabilizes the ³CT state over the lowest energy triplet metal-centered (³MC) state in the ground-state geometry. Single-crystal X-ray diffraction (XRD) and density functional theory (DFT) suggest that formation of this CT state depopulates an orbital with Fe–N_amido antibonding character, causing metal–ligand bonds to contract and accentuating the geometric differences between CT and MC excited states. These effects diminish the driving force for electron transfer to metal-centered excited states and increase the intramolecular reorganization energy, critical properties for extending the lifetime of CT excited states. These findings highlight metal–ligand covalency as a novel design principle for elongating excited state lifetimes in abundant metal photosensitizers.

Precious metal complexes with the d⁶ valence electron configuration often exhibit luminescent metal-to-ligand charge transfer (MLCT) excited states, which form the basis for many applications in lighting, sensing, solar cells and synthetic photochemistry. Iron(ii ) has received much attention as a possible Earth-abundant alternative, but to date no iron(ii) complex has been reported to show MLCT emission upon continuous-wave excitation. Manganese(i) has the same electron configuration as that of iron(ii), but until now has typically been overlooked in the search for cheap MLCT luminophores. Here we report that isocyanide chelate ligands give access to air-stable manganese(i ) complexes that exhibit MLCT luminescence in solution at room temperature. These compounds were successfully used as photosensitizers for energy- and electron-transfer reactions and were shown to promote the photoisomerization of trans-stilbene. The observable electron transfer photoreactivity occurred from the emissive MLCT state, whereas the triplet energy transfer photoreactivity originated from a ligand-centred ³π–π* state.

Competition between entropic and enthalpic factors in an excited-state thermal equilibrium dictates temperature- and solvent-dependent photoluminescence quenching in [Ru(bpy)₂(bpy-cc-AQ)]²⁺.