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Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis

[Image: see text] Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic...

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Autores principales: Schmid, Lucius, Kerzig, Christoph, Prescimone, Alessandro, Wenger, Oliver S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8395604/
https://www.ncbi.nlm.nih.gov/pubmed/34467335
http://dx.doi.org/10.1021/jacsau.1c00137
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author Schmid, Lucius
Kerzig, Christoph
Prescimone, Alessandro
Wenger, Oliver S.
author_facet Schmid, Lucius
Kerzig, Christoph
Prescimone, Alessandro
Wenger, Oliver S.
author_sort Schmid, Lucius
collection PubMed
description [Image: see text] Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with α-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C(6)F(5))(3) groups attached to the CN(–) ligands stabilize the metal-based t(2g)-like orbitals by ∼0.8 eV, leading to high (3)MLCT energies (up to 2.50 eV) that are more typical for cyclometalated iridium(III) complexes. Through variation of their α-diimine ligands, nonradiative excited-state relaxation pathways involving higher-lying metal-centered states can be controlled, and their luminescence quantum yields and MLCT lifetimes can be optimized. These combined properties make the respective isocyanoborato complexes amenable to photochemical reactions for which common ruthenium(II)-based sensitizers are unsuited, due to a lack of sufficient triplet energy or excited-state redox power. Specifically, this includes photoisomerization reactions, sensitization of nickel-catalyzed cross-couplings, pinacol couplings, and oxidative decarboxylative C–C couplings. Our work is relevant in the greater context of tailoring photoactive coordination compounds to current challenges in synthetic photochemistry and solar energy conversion.
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spelling pubmed-83956042021-08-30 Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis Schmid, Lucius Kerzig, Christoph Prescimone, Alessandro Wenger, Oliver S. JACS Au [Image: see text] Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with α-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C(6)F(5))(3) groups attached to the CN(–) ligands stabilize the metal-based t(2g)-like orbitals by ∼0.8 eV, leading to high (3)MLCT energies (up to 2.50 eV) that are more typical for cyclometalated iridium(III) complexes. Through variation of their α-diimine ligands, nonradiative excited-state relaxation pathways involving higher-lying metal-centered states can be controlled, and their luminescence quantum yields and MLCT lifetimes can be optimized. These combined properties make the respective isocyanoborato complexes amenable to photochemical reactions for which common ruthenium(II)-based sensitizers are unsuited, due to a lack of sufficient triplet energy or excited-state redox power. Specifically, this includes photoisomerization reactions, sensitization of nickel-catalyzed cross-couplings, pinacol couplings, and oxidative decarboxylative C–C couplings. Our work is relevant in the greater context of tailoring photoactive coordination compounds to current challenges in synthetic photochemistry and solar energy conversion. American Chemical Society 2021-05-13 /pmc/articles/PMC8395604/ /pubmed/34467335 http://dx.doi.org/10.1021/jacsau.1c00137 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Schmid, Lucius
Kerzig, Christoph
Prescimone, Alessandro
Wenger, Oliver S.
Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title_full Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title_fullStr Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title_full_unstemmed Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title_short Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis
title_sort photostable ruthenium(ii) isocyanoborato luminophores and their use in energy transfer and photoredox catalysis
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8395604/
https://www.ncbi.nlm.nih.gov/pubmed/34467335
http://dx.doi.org/10.1021/jacsau.1c00137
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