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2508001029
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Initiation of Radical Photopolymerization with Perylenebisimide Derivatives Having Twisted Molecular Structures as Heavy-Atom-Free Visible Light-Harvesting Efficient Photoinitiators
  • Wenhui Li 1,   
  • Yuqi Hou 2,   
  • Jianzhang Zhao 1, *

Received: 19 Jun 2025 | Revised: 27 Jul 2025 | Accepted: 29 Jul 2025 | Published: 04 Aug 2025

Abstract

We developed novel visible light-harvesting photoinitiators for radical photopolymerization, based on perylenebisimide (PBI) derivatives having twisted molecular structure and efficient intersystem crossing (ISC). These novel photoinitiators show strong absorption of green light (ε = 6.2 × 104 M−1cm−1 at 654 nm), efficient ISC (singlet oxygen quantum yield ΦΔ is up to 77%), and long-lived triplet excited states (τT is up to 334 μs). Fluorescence and triplet state quenching studies show that the triplet excited states of these photoinitiators play a major role for the intermolecular electron transfer with the co-initiator tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate (NB) to produce the free radicals, supported by the Stern–Volmer quenching constants for the singlet excited state and triplet excited state, which are 72 M−1 and 1.0 × 104 M−1, respectively. Using an alternative co-initiator, diphenyliodonium (DPI), gives much poorer photopolymerization. Interestingly, using two co-initiators of NB and DPI simultaneously in the blends, makes the photopolymerization more efficient and faster, because for the three-component blend, the recombination of electron donor co-initiator NB and electron acceptor co-initiator DPI makes the photoinitiators a photocatalyst, i.e., absorption of one photon will produce two radicals. These results are useful for development of new visible light-absorbing photoinitiators for radical photopolymerization.

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Li, W.; Hou, Y.; Zhao, J. Initiation of Radical Photopolymerization with Perylenebisimide Derivatives Having Twisted Molecular Structures as Heavy-Atom-Free Visible Light-Harvesting Efficient Photoinitiators. PhotoScience Advances 2025, 1 (1), 1.
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