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Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion

[Image: see text] Many Cu(I) complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic Zn(II) compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet...

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Autores principales: Kübler, Jasmin A., Pfund, Björn, Wenger, Oliver S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9597861/
https://www.ncbi.nlm.nih.gov/pubmed/36311829
http://dx.doi.org/10.1021/jacsau.2c00442
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author Kübler, Jasmin A.
Pfund, Björn
Wenger, Oliver S.
author_facet Kübler, Jasmin A.
Pfund, Björn
Wenger, Oliver S.
author_sort Kübler, Jasmin A.
collection PubMed
description [Image: see text] Many Cu(I) complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic Zn(II) compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet π–π* states. We report two closely related tetrahedral Zn(II) compounds, in which intersystem crossing occurs with appreciable quantum yields and leads to the population of triplet excited states with intraligand charge-transfer (ILCT) character. In addition to showing fluorescence from their initially excited (1)ILCT states, these new compounds therefore undergo triplet–triplet energy transfer (TTET) from their (3)ILCT states and consequently can act as sensitizers for photo-isomerization reactions and triplet–triplet annihilation upconversion from the blue to the ultraviolet spectral range. The photoactive (3)ILCT state furthermore facilitates photoinduced electron transfer. Collectively, our findings demonstrate that mononuclear Zn(II) compounds with photophysical and photochemical properties reminiscent of well-known Cu(I) complexes are accessible with suitable ligands and that they are potentially amenable to many different applications. Our insights seem relevant in the greater context of obtaining photoactive compounds based on abundant transition metals, complementing well-known precious-metal-based luminophores and photosensitizers.
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spelling pubmed-95978612022-10-27 Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion Kübler, Jasmin A. Pfund, Björn Wenger, Oliver S. JACS Au [Image: see text] Many Cu(I) complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic Zn(II) compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet π–π* states. We report two closely related tetrahedral Zn(II) compounds, in which intersystem crossing occurs with appreciable quantum yields and leads to the population of triplet excited states with intraligand charge-transfer (ILCT) character. In addition to showing fluorescence from their initially excited (1)ILCT states, these new compounds therefore undergo triplet–triplet energy transfer (TTET) from their (3)ILCT states and consequently can act as sensitizers for photo-isomerization reactions and triplet–triplet annihilation upconversion from the blue to the ultraviolet spectral range. The photoactive (3)ILCT state furthermore facilitates photoinduced electron transfer. Collectively, our findings demonstrate that mononuclear Zn(II) compounds with photophysical and photochemical properties reminiscent of well-known Cu(I) complexes are accessible with suitable ligands and that they are potentially amenable to many different applications. Our insights seem relevant in the greater context of obtaining photoactive compounds based on abundant transition metals, complementing well-known precious-metal-based luminophores and photosensitizers. American Chemical Society 2022-10-11 /pmc/articles/PMC9597861/ /pubmed/36311829 http://dx.doi.org/10.1021/jacsau.2c00442 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Kübler, Jasmin A.
Pfund, Björn
Wenger, Oliver S.
Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title_full Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title_fullStr Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title_full_unstemmed Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title_short Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion
title_sort zinc(ii) complexes with triplet charge-transfer excited states enabling energy-transfer catalysis, photoinduced electron transfer, and upconversion
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9597861/
https://www.ncbi.nlm.nih.gov/pubmed/36311829
http://dx.doi.org/10.1021/jacsau.2c00442
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