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Synthesis 2025; 57(17): 2573-2578
DOI: 10.1055/s-0043-1773518
DOI: 10.1055/s-0043-1773518
paper
Boryl Radical Chemistry
Homolytic Photocleavage of the B–N Bond in N-Heterocyclic Carbene Borane Scaffolds: Towards Efficient Type I Photoinitiators
We thank the Centre National de la Recherche Scientifique (CNRS) and Université de Haute-Alsace (UHA) for funding, as well as the Agence Nationale de la Recherche (ANR) for the grants IMPACT (ANR-11-BS08-0016) and NHCX (ANR-11-BS07-0008).
Abstract
A new family of Type I photoinitiators based on N-heterocyclic carbene borane is introduced. The compounds are synthesized using a previously unknown homolytic B–N cleavage reaction. Three original NHC-amino borane compounds were designed and synthesized, and their UV absorption properties were assessed. All exhibit high molar extinction coefficients and frontier orbitals on the N-atom-bearing group. Their photolysis is rapid. ESR experiments clearly support the B–N homolytic bond cleavage to both NHC-BH2 • and a delocalized radical centered mostly on sulfur. Outstanding polymerization profiles of a benchmark trifunctional acrylate monomer are noted in laminate, where the final acrylate conversions reached 70% with filtered light (λ > 300 nm).
Key words
radical reactions - photochemistry - polymerization - cleavage - N-heterocyclic carbenes - boranesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1773518.
Included are: synthesis of the BN compounds BNa–c; predicted UV/Vis spectra; emission
spectrum of the Xe-Hg lamp; photolysis of other B–N compounds; other B-N structures;
structures predicted by molecular modeling.
- Supporting Information
Publication History
Received: 06 December 2024
Accepted after revision: 06 January 2025
Article published online:
17 February 2025
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