Work

100 μs Luminescence Lifetime Boosts the Excited State Reactivity of a Ruthenium(II)‐Anthracene Complex in Photon Upconversion and Photocatalytic Polymerizations with Red Light

Year: 2024

Type: article

Abstract: The triplet excited state lifetime of a photosensitizer is an essential parameter for diffusion‐controlled energy‐ and electron‐transfer, which occurs usually in a competitive manner to the intrinsic decay of a triplet excited state. Here we show the decisive role of luminescence lifetime in the triplet excited state reactivity toward energy‐ and electron transfer. Anchoring two phenyl anthracene chromophores to a ruthenium(II) polypyridyl complex (RuII ref) leads to a RuII triad with a luminescence lifetime above 100 μs, which is more than 40 times longer than that of the prototypical complex. The obtained RuII triad sensitizes energy transfer to anthracene‐based annihilators more efficiently than RuII ref and enables red‐to‐blue photon upconversion with a pseudo anti‐Stokes shift of 0.94 eV and a moderate upconversion efficiency near 1 % in aerated solution. Particularly, RuII triad allows rapid photoredox catalytic polymerizations of acrylate and acrylamide monomers under aerobic condition with red light, which are kinetically hindered for RuII ref. Our work shows that excited state lifetime of a photosensitizer governs the dynamics of the excited state reactions, which seems an overlooked but important aspect for photochemistry.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202402679

Authors: Heinrich Hammecke, Dennis Fritzler, Nikita Vashistha, Pengyue Jin, Benjamin Dietzek‐Ivanšić, Cui Wang

Institutions: Osnabrück University, Leibniz Institute of Photonic Technology, Friedrich Schiller University Jena

Language: English

Topic: Photochemistry and Electron Transfer Studies

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,640

Funder: Deutsche Forschungsgemeinschaft