Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields
Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields
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通过单线态氧产率预测三线态量子产率的经验 DFT 模型
DOI：
10.1002/cptc.202100205
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发表时间：
2022
期刊：
影响因子：
3.7
通讯作者：
McCormick, Theresa M.
中科院分区：
文献类型：
--
作者：
Steinkamp, Bret A.;Lutkus, Luke V.;Lewis, Rob;McCormick, Theresa M.
三重态光敏剂可用于各种应用，包括光催化、有机发光二极管和光动力疗法。激发态三重态可以被三重态氧猝灭，生成单重态氧。通常，单重态氧量子产率(Φ▵)被用作三重态产额的较低近似值。即使是微小的结构变化，其不可预测的影响也会极大地改变Φ▵，并使新的三重态光敏剂的设计复杂化。最常见的提高Φ▵的策略是加入重原子，促进“重原子效应”。然而，重原子的位置和同一性对Φ▵有很大影响。我们已经建立了一个预测模型，将计算出的对光敏剂前线分子轨道有贡献的重原子(S)的自然原子轨道组成与实验Φ▵相关联。该模型由几种荧光素衍生物衍生而来，计算出的Φ▵与各种著名光敏剂的实验值一致，包括罗丹明染料、荧光素衍生物和八面体金属络合物。
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.