Title

Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields

Published In

Chemphotochem

Document Type

Citation

Publication Date

1-5-2022

Abstract

Triplet photosensitizers can be used for a variety of applications, including photocatalysis, OLEDs, and photodynamic therapy. Excited triplet states can be quenched by triplet oxygen to make singlet oxygen. Often the singlet oxygen quantum yield (Φ▵) is used as a lower approximation for the triplet yield. Unpredictable effects of even minor structural changes can drastically alter the Φ▵ and complicate the design of new triplet photosensitizers. The most common strategy to increase Φ▵ is to incorporate heavy atoms, promoting the “heavy atom effect”. However, the position and the identity of the heavy atom greatly influences the Φ▵. We have created a predictive model that correlates calculated natural atomic orbital composition of the heavy atom(s) contributing to the frontier molecule orbitals of a photosensitizer with the experimental Φ▵. The model, derived from several fluorescein derivatives, provides a calculated Φ▵ in agreement with the experimental values for a variety of well-known photosensitizers, including rhodamine dyes, fluorescein derivatives, and octahedral metal complexes.

Rights

Copyright © 1999-2022 John Wiley & Sons, Inc. All rights reserved

DOI

10.1002/cptc.202100205

Persistent Identifier

https://archives.pdx.edu/ds/psu/36989

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