The spin-vibronic effect (SVE) accelerates quantum-mechanically forbidden electronic transitions, but experimental manifestations of this phenomenon remain limited. In this contribution, the role of SVE in photoinduced electron transfer (PET) dynamics is probed by coherent vibrational wavepacket (CVWP) motions in Pt(II) dimer-naphthalene diimide donor–acceptor complexes. Metal–metal-to-ligand charge-transfer (MMLCT) excitation of the donor triggers ballistic PET, driving the molecule away from equilibrium. The SVE then directs the PET trajectory from the 1MMLCT excited state to an intermediate ligand-centered triplet state, modulating the CVWP dynamics along the reaction coordinates. Herzberg–Teller type oscillations indicate that the Pt–Pt stretching vibration, arising from the formation of the excited triplet intermediate, serves as the reaction coordinate for charge separation. Our experimental findings advance the understanding of the interplay between electronic, vibrational, and spin degrees of freedom in ultrafast photoactivated processes.

Precise, sustainable, and scalable bandgap tuning of metal halide perovskite (MHP) nanocrystals (NCs) is critical for their integration into advanced optoelectronic and photocatalytic systems. Photoin...

Performance of solid-state triplet fusion upconversion films is enhanced by surface plasmons, intensity threshold is reduced by a factor of 17 and external quantum efficiency is enhanced by a factor o...

Catalytic CO2 reduction reactions featuring high selectivity toward formate are relatively rare. In some homogeneous molecular CO2-reducing electrocatalysis, using triethylamine (TEA) and isopropanol ...

The oxidation of metal-aquo and -hydroxo complexes to generate the high-valent metal-oxo species used in oxidative catalysis is often kinetically slow due to sluggish proton transfer between ligated −H2O/–OH in the proton-coupled electron transfer (PCET) chemistry. In this research, a ruthenium water oxidation catalyst anchored to a conductive tin-doped indium oxide (ITO) thin film, abbreviated ITO|RuII–OH2, was characterized by spectroscopic and electrochemical methods in acetate or phosphate buffers. The deprotonated intermediate, RuII–OH, was observed spectroscopically in the PCET half-reaction ITO(e–)|RuIII–OH + H+ → ITO|RuII–OH2 indicating an underlying stepwise ET-PT mechanism. In contrast, at elevated buffer concentrations, this intermediate was absent, and a 2–4 order of magnitude increase in the proton transfer rate constant was observed. Kinetic data for this PCET reaction measured as a function of the driving force provided the reorganization energy λ = 1.05 eV and was assigned to a concerted electron–proton transfer (EPT) mechanism. In addition, the standard heterogeneous rate constants for two PCET equilibria, RuIII–OH + H+ + e– ⇌ RuII–OH2 and RuIV = O + H+ + e– ⇌ RuIII–OH were enhanced by these same buffers. Collectively, the data show that the added buffers can enhance the kinetics and thermodynamics for PCET reactions relevant to oxidative catalysis.

We present the first examples of installing a redox reporter and CO2 reduction (CO2R) catalyst onto freshly HF-etched Si (photo)electrodes using a solution-phase nitrocyclocondensation (NCC) reaction....