Theoretical Insight into the Effect of Phosphorus Oxygenation on Nonradiative Decays: Comparative Analysis of P-Bridged Stilbene Analogs

IF 3.7 Q2 CHEMISTRY, PHYSICAL ACS Physical Chemistry Au Pub Date : 2023-10-24 DOI:10.1021/acsphyschemau.3c00038
Naoto Inai*, Shigehiro Yamaguchi* and Takeshi Yanai*, 
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Abstract

Incorporation of the phosphorus element into a π-conjugated skeleton offers valuable prospects for adjusting the electronic structure of the resulting functional π-electron systems. Trivalent phosphorus has the potential to decrease the LUMO level through σ*−π* interaction, which is further enhanced by its oxygenation to the pentavalent P center. This study shows that utilizing our computational analysis to examine excited-state dynamics based on radiative/nonradiative rate constants and fluorescence quantum yield (ΦF) is effective for analyzing the photophysical properties of P-containing organic dyes. We theoretically investigate how the trivalent phosphanyl group and pentavalent phosphine oxide moieties affect radiative and nonradiative decay processes. We evaluate four variations of P-bridged stilbene analogs. Our analysis reveals that the primary decay pathway for photoexcited bis-phosphanyl-bridged stilbene is the intersystem crossing (ISC) to the triplet state and nonradiative. The oxidation of the phosphine moiety, however, suppresses the ISC due to the relative destabilization of the triplet states. The calculated rate constants match an increase in experimental ΦF from 0.07 to 0.98, as simulated from 0.23 to 0.94. The reduced HOMO–LUMO gap supports a red shift in the fluorescence spectra relative to the phosphine analog. The thiophene-fused variant with the nonoxidized trivalent P center exhibits intense emission with a high ΦF, 0.95. Our prediction indicates that the ISC transfer is obstructed owing to the relatively destabilized triplet state induced by the thiophene substitution. Conversely, the thiophene-fused analog with the phosphine oxide moieties triggers a high-rate internal conversion mediated by conical intersection, leading to a decreased ΦF.

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磷氧化对非辐射衰变影响的理论洞察:p -桥式二苯乙烯类似物的比较分析
在π共轭骨架中加入磷元素,为调整所得到的功能π电子体系的电子结构提供了有价值的前景。三价磷具有通过σ*−π*相互作用降低LUMO能级的潜力,而其与五价P中心的氧化作用进一步增强了这一作用。本研究表明,利用我们的计算分析来检查基于辐射/非辐射速率常数和荧光量子产率(ΦF)的激发态动力学是分析含磷有机染料的光物理性质的有效方法。我们从理论上研究了三价磷酰基团和五价氧化磷基团如何影响辐射和非辐射衰变过程。我们评估了四种变化的p桥苯乙烯类似物。我们的分析表明,光激发双磷酰桥接苯乙烯的主要衰变途径是系统间交叉(ISC)到三重态和非辐射。然而,由于三重态的相对不稳定,磷化氢部分的氧化抑制了ISC。计算出的速率常数与实验值ΦF从0.07增加到0.98相匹配,模拟值从0.23增加到0.94。相对于磷化氢类似物,减少的HOMO-LUMO间隙支持荧光光谱中的红移。具有非氧化三价P中心的噻吩熔合变体具有高ΦF, 0.95的强发射。我们的预测表明,由于噻吩取代引起的相对不稳定的三重态,阻碍了ISC的转移。相反,噻吩与氧化膦部分融合的类似物触发由锥形交叉介导的高速率内部转换,导致ΦF降低。
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期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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