Toward Quantitative Prediction of Fluorescence Quantum Efficiency by Combining Direct Vibrational Conversion and Surface Crossing: BODIPYs as an Example

Ou, Qi; Peng, Qian; Shuai, Zhigang

doi:10.1021/acs.jpclett.0c02054

Cited by 64 publications

(70 citation statements)

References 62 publications

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“…The BODIPY pigment and its derivatives are key entities for phototheranostics [1], including photodynamic therapy [2], functional optoelectronic materials [3], such as solar cells [4][5][6] and light emitting diodes [7], and stimuli-responsive materials [8][9][10][11]. In order to understand or predict the optical properties [12,13] of such important chromophore, and notably the lowest energy electronic transition, a very large number of investigations involving computational argumentations were reported but most of the time the correspondence between the calculated position and experimentally observed one turned out to be chronically poor, where differences ranging from 60 to 100 nm were commonly depicted [14][15][16][17][18][19][20][21][22][23][24][25][26][27]. However, on some rare occasions, the comparison between computations and experiments appeared much better [28,29].…”

Section: Introductionmentioning

confidence: 99%

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

et al. 2021

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The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common “fudge” correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature.

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Section: Introductionmentioning

confidence: 99%

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

et al. 2021

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“…To understand these effects, many theoretical studies have been carried out on both BODIPYs and Aza‐BODIPYs 9–18 . In many of these studies, time‐dependent density functional theory (TD‐DFT) was the method of choice; however, some recent studies tested different coupled‐cluster approaches 9,10,16–18 as well as other methods, for example, the Bethe‐Salpeter formalism combined with TD‐DFT 19 and the spin‐flip TD‐DFT approach 20 . The latter two methods offer computationally cheaper alternatives to multireference and coupled‐cluster approaches but can be more accurate than “pure” TD‐DFT.…”

Section: Introductionmentioning

confidence: 99%

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Feldt¹,

Brown

2020

J Comput Chem

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It was previously reported that Laplace transformed local CC2 (LCC2*) provided the best agreement (MAE = 0.145 eV) when comparing vertical excitation energies to experimental λ max for a benchmark set of 17 BODIPY/Aza-BODIPY molecules. However, these energies did not agree with values obtained from canonical CC2. Here we report LCC2* computations of vertical excitation energies on the same benchmark set of molecules using a newly implemented treatment of the ground state. Comparison with resolution-of-identity approximate coupled cluster to second-order (RI-CC2) results demonstrate that the new LCC2* results agree quantitatively. Furthermore, these values can easily be corrected empirically to also provide excellent agreement with the experiment. We show that the local algebraic diagrammatic construction to second-order (LADC(2)) method exhibits the same differences between implementations as seen for LCC2. The source of the difference is traced to an improved treatment of the ground state in the local methods, which decreases agreement with the experiment (as attributed to a fortuitous cancellation of errors) but significantly improves agreement with RI-CC2. While the absolute vertical excitation energies now show larger deviations, there remains a strong linear correlation between the LCC2* results and the experiment. For the 17 BODIPY/Aza-BODIPY molecules vertical excitation energies are determined using DLPNO-STEOM-CCSD and shown to have excellent agreement with experimental λ max (MAE = 0.145 eV), which is the best of all the single-reference methods. The vertical excitation energies are determined using LCC2*, empirically corrected LCC2*, and RI-CC2 for a series of eight large BODIPYs and Aza-BODIPYs.

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“…Reproduced with permission from Ref. [54] Copyright 2020 American Chemical Society solution or in solid phase according to the good linear relationship between the calculated and experimental Φ LQY .…”

Section: Hindrance Of Nonradiative Channels In Aggregates the Quantitative Calculation Of Quantum Luminescence Yieldmentioning

confidence: 99%

Molecular mechanism of aggregation‐induced emission

2021

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Deep understanding of the inherent luminescence mechanism is essential for the development of aggregation-induced emission (AIE) materials and applications. We first note that the intermolecular excitonic coupling is much weaker in strength than the intramolecular electron-vibration coupling for a majority of newly termed AIEgens, which leads to the emission peak position insensitive to excitonic coupling, hence the conventional excitonic model for J-aggregation cannot effectively explain their AIE phenomena. Then, using multiscale computational approach coupled with our self-developed thermal vibration correlation function rate formalism and transition-state theory, we quantitatively investigate the aggregation effect on both the radiative and the nonradiative decays of molecular excited states. For radiative decay processes, we propose that the lowest excited state could convert from a transition dipole-forbidden "dark" state to a dipole-allowed "bright" state upon aggregation. For the radiationless processes, we demonstrate the blockage of nonradiative decay via vibration relaxation (BNR-VR) in harmonic region or the removal of nonradiative decay via isomerization (RNR-ISO) or minimum energy crossing point (RNR-MECP) beyond harmonic region in a variety of AIE aggregates. Our theoretical work not only justifies a plethora of experimental results but also makes reliable predictions on molecular design and mechanism that can be experimentally verified. Looking forward, we believe this review will benefit the deep understanding about the universality of AIE phenomenon and further extending the scope of AIE systems with novel applications.

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Toward Quantitative Prediction of Fluorescence Quantum Efficiency by Combining Direct Vibrational Conversion and Surface Crossing: BODIPYs as an Example

Cited by 64 publications

References 62 publications

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Molecular mechanism of aggregation‐induced emission

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