Thermally Activated Delayed Fluorescence Mechanism of a Bicyclic "Carbene-Metal-Amide" Copper Compound : DFT/MRCI Studies and Roles of Excited-State Structure Relaxation
Herein we investigated the luminescence mechanism of one "carbene-metal-amide" copper compound with thermally activated delayed fluorescence (TADF) using density functional theory (DFT)/multireference configuration interaction, DFT, and time-dependent DFT methods with the polarizable continuum model. The experimentally observed low-energy absorption and emission peaks are assigned to the S1 state, which exhibits clear interligand and partial ligand-to-metal charge-transfer character. Moreover, it was found that a three-state (S0, S1, and T1) model is sufficient to describe the TADF mechanism, and the T2 state should play a negligible role. The calculated S1-T1 energy gap of 0.10 eV and proper spin-orbit couplings facilitate the reverse intersystem crossing (rISC) from T1 to S1. At 298 K, the rISC rate of T1 → S1 (∼106 s-1) is more than 3 orders of magnitude larger than the T1 phosphorescence rate (∼103 s-1), thereby enabling TADF. However, it disappears at 77 K because of a very slow rISC rate (∼101 s-1). The calculated TADF rate, lifetime, and quantum yield agree very well with the experimental data. Methodologically, the present work shows that only considering excited-state information at the Franck-Condon point is insufficient for certain emitting systems and including excited-state structure relaxation is important.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2022 |
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| Erschienen: |
2022 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:61 |
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| Enthalten in: |
Inorganic chemistry - 61(2022), 20 vom: 23. Mai, Seite 7673-7681 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Song, Xiu-Fang [VerfasserIn] |
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| Links: |
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| Themen: |
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| Anmerkungen: |
Date Revised 23.05.2022 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.1c03603 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM337316392 |
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| 100 | 1 | |a Song, Xiu-Fang |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Thermally Activated Delayed Fluorescence Mechanism of a Bicyclic "Carbene-Metal-Amide" Copper Compound |b DFT/MRCI Studies and Roles of Excited-State Structure Relaxation |
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| 500 | |a Date Revised 23.05.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Herein we investigated the luminescence mechanism of one "carbene-metal-amide" copper compound with thermally activated delayed fluorescence (TADF) using density functional theory (DFT)/multireference configuration interaction, DFT, and time-dependent DFT methods with the polarizable continuum model. The experimentally observed low-energy absorption and emission peaks are assigned to the S1 state, which exhibits clear interligand and partial ligand-to-metal charge-transfer character. Moreover, it was found that a three-state (S0, S1, and T1) model is sufficient to describe the TADF mechanism, and the T2 state should play a negligible role. The calculated S1-T1 energy gap of 0.10 eV and proper spin-orbit couplings facilitate the reverse intersystem crossing (rISC) from T1 to S1. At 298 K, the rISC rate of T1 → S1 (∼106 s-1) is more than 3 orders of magnitude larger than the T1 phosphorescence rate (∼103 s-1), thereby enabling TADF. However, it disappears at 77 K because of a very slow rISC rate (∼101 s-1). The calculated TADF rate, lifetime, and quantum yield agree very well with the experimental data. Methodologically, the present work shows that only considering excited-state information at the Franck-Condon point is insufficient for certain emitting systems and including excited-state structure relaxation is important | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Li, Zi-Wen |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Wen-Kai |e verfasserin |4 aut | |
| 700 | 1 | |a Gao, Yuan-Jun |e verfasserin |4 aut | |
| 700 | 1 | |a Cui, Ganglong |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d 1966 |g 61(2022), 20 vom: 23. Mai, Seite 7673-7681 |w (DE-627)NLM110650298 |x 1520-510X |7 nnns |
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