Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields
Sponsor
This work was funded by the American National Science Foundation, Directorate for Mathematical and Physical Science, Division of Chemistry, award #1800599. The National Science Foundation is acknowledged for support of the Bio Analytical Mass Spectrometry Facility at PSU (MRI1828573). Funding was also provided from the Portland State University Faculty Development Grant.
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
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DOI
10.1002/cptc.202100205
Persistent Identifier
https://archives.pdx.edu/ds/psu/36989
Citation Details
McCormick, T., Steinkamp, B. A., Lutkus, L. V., & Lewis, R. Empirical DFT model to predict triplet quantum yield through singlet‐oxygen yields. ChemPhotoChem.