ArticleSmall (Weinheim an der Bergstrasse, Germany)2026
Triplet Energy Transfer Strategy for Visible Light Activation of Bio-Based Oxime Esters in Photopolymerization and 3D Printing.
Article in Small (Weinheim an der Bergstrasse, Germany), 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Visible-light and solar photopolymerization require photoinitiating systems that combine high reactivity, formulation stability, and biological safety. Here, we present a triplet energy transfer strategy that couples bio-based benzoyl oxime esters, prepared from bio-derived aldehydes, with the high-triplet-energy visible sensitizer 2-isopropylthioxanthone (ITX), converting UV-absorbing oxime ester scaffolds into efficient metal-free photoinitiators for 405 nm LED and sunlight irradiation. Quantum chemical calculations, electrochemical analysis, laser flash photolysis, ESR spin trapping, and in situ FTIR reveal that Dexter-type triplet-triplet energy transfer from ITX selectively populates the reactive triplet states of the oxime esters, while the electron pathway is disfavored. Subsequent N─O bond cleavage and rapid decarboxylation generate initiating phenyl radicals. The BE2+ITX formulation affords faster curing, higher conversion, and deeper through-cure than BE2 or ITX alone, while matching or surpassing benchmark onium and amine systems with favorable cytocompatibility and storage stability. This triplet-energy-driven design rule enables modular development of greener photoinitiators for high-resolution 3D printing and ambient curing.
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