Is faster always better? Rethinking quenching and rate orchestration in photochemical catalysis
(2026) Chem Catalysis — Vol. 6, n° 7, p. 101782 (2026)
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- Joffrey Scriven is a FRIA PhD student at UCLouvain, where his research focuses on mechanistic photoredox catalysis and the synthesis of novel chromium-based photosensitizers. Felix Glaser earned his PhD in 2022 from the University of Basel, where he worked with Prof. O. Wenger on mechanistic photoredox catalysis. After conducing his postdoctoral research on coulombic dyads for energy-transfer applications with Prof. C. Kerzig at the University of Mainz, he joined UCLouvain in 2023 as an F.R.S.-FNRS chargé de recherches (postdoctoral researcher) and now develops innovative iron-based dyads for electron and energy-transfer applications. Ludovic Troian-Gautier is an F.R.S.-FNRS chercheur qualifié (research associate) at UCLouvain and an investigator at the Wel Research Institute, where he leads a research program centered around understanding key fundamental processes that govern excited-state reactivity. Research in his group spans several areas, including excited-state reactivity and charge separation, light-driven solar-fuel production, and mechanistic photoredox catalysis using organic dyes and complexes based on scarce and earth-abundant transition metals. The use of light to trigger organic reactions represents one of the most remarkable conceptual breakthroughs of the 20 th century. 1,2 Among the earliest visionary demonstrations, foreseeing the potential of solar-driven synthesis, Ciami-cian and Silber employed ultraviolet sunlight to convert camphor into car-vone. 3 These transformations, however, required months of irradiation and suffered from low selectivity, inefficient photon utilization, and intermittent exposure. Initially centered on the photophysi-cal properties of organic chromophores and photoactive metal complexes in the late 20 th century, the field has since grown into a thriving area of research as a result of technological and scientific progress. The development of light bulbs, followed by wavelength-selective irradiation sources and eventually high-power light-emitting diodes (LEDs) and continuous-wave lasers spanning the visible spectrum, transformed photochemistry from an empirical discipline into a controllable synthetic methodology. Alongside these technological advances, mechanistic photochemistry matured through a close dialogue between synthetic and physical chemists seeking quantitative descriptions of excited-state reactivity. Together, these advances yielded mechanistic insights into the underlying processes, enabling the more rational design of new photochemical systems. Combined with advances in time-resolved spectroscopy, precise regulation of spectral distribution and photon flux enabled quantitative measurements of excited-state lifetimes, quenching kinetics, and electron-transfer rates. This integration of technological and mechanistic progress established a framework in which photochemical reactivity could be rationalized through measurable kinetic parameters rather than qualitative observation. A key concept in this mechanistic framework is the century-old Stern-Volmer model introduced by Otto Stern and Max Volmer. 4 In its classical form, the relationship between luminescence intensity (I) or excited-state lifetime (τ) and quencher concentration is expressed as shown in Equation 1, where I 0 and I are the emission intensities in the absence and presence, respectively, of the quencher; τ 0 and τ are the excited-state lifetimes in the absence and presence , respectively, of the quencher; [Q] is the quencher concentration; and K SV is the Stern-Volmer constant. I 0 I = τ 0 τ = 1 + K SV [Q] = 1 + k q τ 0 [Q] Equation 1 From this expression, the diffusional bimolecular quenching rate constant (k q) can be extracted. However, this classical treatment implicitly assumes purely dynamic quenching and neglects contributions from ground-state association. In the presence of static quenching, From left to right: Please cite this article in press as: Scriven et al., Is faster always better? Rethinking quenching and rate orchestration in photochemical catal-ysis, Chem Catalysis (2026), https://doi.
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Scriven, J., Glaser, F., & Troian-Gautier, L. (2026). Is faster always better? Rethinking quenching and rate orchestration in photochemical catalysis. Chem Catalysis, 6(7), 101782. https://doi.org/10.1016/j.checat.2026.101782 (Original work published 2026)