Nature of excited-state dependent hydrogen bonds and their critical role in determining the photophysical properties of aromatic thioketones

Literature Information

Publication Date 2022-06-24
DOI 10.1039/D2CP02016E
Impact Factor 3.676
Authors

Wei-Hai Fang


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Abstract

In this work, how the excited-state dependent hydrogen bond (H-bond) interactions control photophysical processes have been uncovered by accurate electronic structure calculations for the five lowest-lying states (S0, S1, S2, T1, and T2) of three aromatic thioketones and their isomers. The difference in the H-bond nature between S2 and S1 gives rise to ultrafast S2 → S1 internal conversion via the two-state conical intersection. Strong S2 fluorescence observed usually in thiocarbonyl compounds is absent in aromatic thioketones with intramolecular H-bonds. Meanwhile, the relatively weak H-bond interactions in S1 and T1 states make the S1, T2, and T1 states degenerate or quasi-degenerate. As a result, the T2 state acts as a relay and enables both forward S1 → T1 and reverse T1 → S1 processes to occur efficiently, which provides new insights into the mechanism of thermally activated delayed fluorescence (TADF), and could be used to improve the design principle of purely organic TADF materials.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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