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 apr 2022
Accepted
04 jún 2022
First published
24 jún 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements