Issue 26, 2022

Donor modification of thermally activated delayed fluorescence photosensitizers for organocatalyzed atom transfer radical polymerization

Abstract

Thermally activated delayed fluorescence (TADF) photosensitizers based on 9,10-dihydro-9,9-dimethylacridine/2,4,6-triphenylpyrimidine conjugates with strong visible absorption, large excited state reduction potentials, and long-lived triplet excited states were successfully employed in the organocatalyzed atom transfer radical polymerization (O-ATRP) of methacrylic monomers. A donor-modification strategy dramatically improved the stability of the photocatalyst radical cations, while retaining their high oxidizing strengths, a key requirement for controlled O-ATRP. Time-resolved photoluminescence studies of the catalysts support initiation by electron transfer from both singlet and triplet states, with functionalized donors producing higher driving forces for photoinduced electron transfer. A donor-modified TADF photocatalyst was found for the synthesis of methacrylic polymers with Đ below 1.3 at catalyst loadings down to 50 ppm. This catalyst was also successfully applied in block copolymer synthesis, while the unfunctionalized analogue yields entirely uncontrolled polymerization.

Graphical abstract: Donor modification of thermally activated delayed fluorescence photosensitizers for organocatalyzed atom transfer radical polymerization

Supplementary files

Article information

Article type
Paper
Submitted
12 Eph 2022
Accepted
04 Jun 2022
First published
24 Jun 2022

Polym. Chem., 2022,13, 3892-3903

Donor modification of thermally activated delayed fluorescence photosensitizers for organocatalyzed atom transfer radical polymerization

A. M. Polgar, S. H. Huang and Z. M. Hudson, Polym. Chem., 2022, 13, 3892 DOI: 10.1039/D2PY00470D

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