Sustainable Visible-Light Photoinitiation Enabled by a Bio-Based Photosensitizer/Oxime Ester Combination via Triplet–Triplet Energy Transfer
Abstract
AC:AC:Visible-light photopolymerization offers safer processing, lower energy input, and broader compatibility with advanced manufacturing than thermally initiated curing or short-wavelength UV processes. However, sustainable photoinitiating systems that operate efficiently under visible light remain limited. Here, a sustainable two-component strategy is reported by combining bio-derived oxime esters with natural or bio-inspired photosensitizers for 405 nm curing. Among the systems investigated, the synthesized oxime ester (OXE1) and menadione (MD, vitamin K3) pair show the best performance, enabling rapid photopolymerization of TMPTA with good formulation homogeneity, low coloration, and good storage stability. Electrochemical analysis and excited-state energetics indicate that direct single-electron transfer between MD and OXE1 is thermodynamically unfavorable. In contrast, steady-state photolysis, laser flash photolysis, CO2 evolution, and ESR spin trapping support a triplet–triplet energy transfer pathway, followed by N–O bond cleavage and decarboxylation, to generate initiating radicals. This work establishes a simple sensitization principle for converting UV-responsive bio-derived oxime esters into visible-light photoinitiators and provides a sustainable design strategy for photopolymerization and 3D microfabrication.
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BibTeX
@article{yang2026sustainable,
title = {{Sustainable Visible-Light Photoinitiation Enabled by a Bio-Based Photosensitizer/Oxime Ester Combination via Triplet–Triplet Energy Transfer}},
author = {Kaidan Yang and Margot Manivel and Coralie Ohl and Céline Dietlin and Fabrice Morlet-Savary and Michael Schmitt and Jean-Patrick Joly and Jing Zhang and Pu Xiao and Jacques Lalevée},
journal = {ACS Applied Materials \& Interfaces},
year = {2026},
month = jul,
doi = {10.1021/acsami.6c13183},
url = {https://hal.science/hal-05743775v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Sustainable Visible-Light Photoinitiation Enabled by a Bio-Based Photosensitizer/Oxime Ester Combination via Triplet–Triplet Energy Transfer
AU - Kaidan Yang
AU - Margot Manivel
AU - Coralie Ohl
AU - Céline Dietlin
AU - Fabrice Morlet-Savary
AU - Michael Schmitt
AU - Jean-Patrick Joly
AU - Jing Zhang
AU - Pu Xiao
AU - Jacques Lalevée
PY - 2026
DA - 2026/07/23
JO - ACS Applied Materials & Interfaces
DO - 10.1021/acsami.6c13183
UR - https://hal.science/hal-05743775v1
AB - AC:AC:Visible-light photopolymerization offers safer processing, lower energy input, and broader compatibility with advanced manufacturing than thermally initiated curing or short-wavelength UV processes. However, sustainable photoinitiating systems that operate efficiently under visible light remain limited. Here, a sustainable two-component strategy is reported by combining bio-derived oxime esters with natural or bio-inspired photosensitizers for 405 nm curing. Among the systems investigated, the synthesized oxime ester (OXE1) and menadione (MD, vitamin K3) pair show the best performance, enabling rapid photopolymerization of TMPTA with good formulation homogeneity, low coloration, and good storage stability. Electrochemical analysis and excited-state energetics indicate that direct single-electron transfer between MD and OXE1 is thermodynamically unfavorable. In contrast, steady-state photolysis, laser flash photolysis, CO2 evolution, and ESR spin trapping support a triplet–triplet energy transfer pathway, followed by N–O bond cleavage and decarboxylation, to generate initiating radicals. This work establishes a simple sensitization principle for converting UV-responsive bio-derived oxime esters into visible-light photoinitiators and provides a sustainable design strategy for photopolymerization and 3D microfabrication.
SN - 1944-8244
SN - 1944-8252
ER -