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Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation

The trifluoromethyl group has been previously explored as a non-conjugated electron-withdrawing group in donor–acceptor thermally activated delayed fluorescence (TADF) emitters. In the present study, we investigate computationally the potential of other fluorine-containing acceptors, trifluoromethox...

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Autores principales: Chen, Dongyang, Zysman-Colman, Eli
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7849250/
https://www.ncbi.nlm.nih.gov/pubmed/33564331
http://dx.doi.org/10.3762/bjoc.17.21
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author Chen, Dongyang
Zysman-Colman, Eli
author_facet Chen, Dongyang
Zysman-Colman, Eli
author_sort Chen, Dongyang
collection PubMed
description The trifluoromethyl group has been previously explored as a non-conjugated electron-withdrawing group in donor–acceptor thermally activated delayed fluorescence (TADF) emitters. In the present study, we investigate computationally the potential of other fluorine-containing acceptors, trifluoromethoxy (OCF(3)), trifluoromethylthio (SCF(3)), and pentafluorosulfanyl (SF(5)), within two families of donor–acceptor TADF emitters. Time-dependent density functional theory calculations indicate that when only two ortho-disposed carbazole donors are used (Type I molecules), the lowest-lying triplet state possesses locally excited (LE) character while the lowest-lying singlet state possesses charge-transfer character. When five carbazole donors are present in the emitter design (Type II molecules), now both S(1) and T(1) states possess CT character. For molecules 2CzOCF(3) and 5CzOCF(3), the singlet energies are predicted to be 3.92 eV and 3.45 eV; however, the singlet-triplet energy gaps, ΔE(ST)s, are predicted to be large at 0.46 eV and 0.37 eV, respectively. The compounds 2CzCF(3), 2CzSCF(3), and 2CzSF(5), from Type I molecules, show significant promise as deep blue TADF emitters, possessing high calculated singlet energies in the gas phase (3.62 eV, 3.66 eV, and 3.51 eV, respectively) and small, ΔE(ST)s, of 0.17 eV, 0.22 eV, and 0.07 eV, respectively. For compounds 5CzSCF(3) and 5CzSF(5), from Type II molecules, the singlet energies are stabilized to 3.24 eV and 3.00 eV, respectively, while ΔE(ST)s are 0.27 eV and 0.12 eV, respectively, thus both show promise as blue or sky-blue TADF emitters. All these six molecules possess a dense number of intermediate excited states between S(1) and T(1), thus likely leading to a very efficient reverse intersystem crossing in these compounds.
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spelling pubmed-78492502021-02-08 Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation Chen, Dongyang Zysman-Colman, Eli Beilstein J Org Chem Full Research Paper The trifluoromethyl group has been previously explored as a non-conjugated electron-withdrawing group in donor–acceptor thermally activated delayed fluorescence (TADF) emitters. In the present study, we investigate computationally the potential of other fluorine-containing acceptors, trifluoromethoxy (OCF(3)), trifluoromethylthio (SCF(3)), and pentafluorosulfanyl (SF(5)), within two families of donor–acceptor TADF emitters. Time-dependent density functional theory calculations indicate that when only two ortho-disposed carbazole donors are used (Type I molecules), the lowest-lying triplet state possesses locally excited (LE) character while the lowest-lying singlet state possesses charge-transfer character. When five carbazole donors are present in the emitter design (Type II molecules), now both S(1) and T(1) states possess CT character. For molecules 2CzOCF(3) and 5CzOCF(3), the singlet energies are predicted to be 3.92 eV and 3.45 eV; however, the singlet-triplet energy gaps, ΔE(ST)s, are predicted to be large at 0.46 eV and 0.37 eV, respectively. The compounds 2CzCF(3), 2CzSCF(3), and 2CzSF(5), from Type I molecules, show significant promise as deep blue TADF emitters, possessing high calculated singlet energies in the gas phase (3.62 eV, 3.66 eV, and 3.51 eV, respectively) and small, ΔE(ST)s, of 0.17 eV, 0.22 eV, and 0.07 eV, respectively. For compounds 5CzSCF(3) and 5CzSF(5), from Type II molecules, the singlet energies are stabilized to 3.24 eV and 3.00 eV, respectively, while ΔE(ST)s are 0.27 eV and 0.12 eV, respectively, thus both show promise as blue or sky-blue TADF emitters. All these six molecules possess a dense number of intermediate excited states between S(1) and T(1), thus likely leading to a very efficient reverse intersystem crossing in these compounds. Beilstein-Institut 2021-01-21 /pmc/articles/PMC7849250/ /pubmed/33564331 http://dx.doi.org/10.3762/bjoc.17.21 Text en Copyright © 2021, Chen and Zysman-Colman https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjoc/terms/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the author(s) and source are credited and that individual graphics may be subject to special legal provisions. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms/terms)
spellingShingle Full Research Paper
Chen, Dongyang
Zysman-Colman, Eli
Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title_full Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title_fullStr Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title_full_unstemmed Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title_short Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation
title_sort exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by td-dft calculation
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7849250/
https://www.ncbi.nlm.nih.gov/pubmed/33564331
http://dx.doi.org/10.3762/bjoc.17.21
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