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Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands

[Image: see text] The synthesis, structure, photophysical properties, and electrochemistry of the first series of Pt(IV) tris-chelates bearing cyclometalated aryl-NHC ligands are reported. The complexes have the general formula [Pt(trz)(2)(C∧N)](+), combining two units of the cyclometalated, mesoion...

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Autores principales: Vivancos, Ángela, Bautista, Delia, González-Herrero, Pablo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9377419/
https://www.ncbi.nlm.nih.gov/pubmed/35860839
http://dx.doi.org/10.1021/acs.inorgchem.2c02039
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author Vivancos, Ángela
Bautista, Delia
González-Herrero, Pablo
author_facet Vivancos, Ángela
Bautista, Delia
González-Herrero, Pablo
author_sort Vivancos, Ángela
collection PubMed
description [Image: see text] The synthesis, structure, photophysical properties, and electrochemistry of the first series of Pt(IV) tris-chelates bearing cyclometalated aryl-NHC ligands are reported. The complexes have the general formula [Pt(trz)(2)(C∧N)](+), combining two units of the cyclometalated, mesoionic aryl-NHC ligand 4-butyl-3-methyl-1-phenyl-1H-1,2,3-triazol-5-ylidene (trz) with a cyclometalated 2-arylpyridine [C∧N = 2-(2,4-difluorophenyl)pyridine (dfppy), 2-phenylpyridine (ppy), 2-(p-tolyl)pyridine (tpy), 2-(2-thienyl)pyridine (thpy), 2-(9,9-dimethylfluoren-2-yl)pyridine (flpy)], and presenting a mer arrangement or metalated aryls. They exhibit a significant photostability under UV irradiation and long-lived phosphorescence in the blue to yellow color range, arising from (3)LC excited states involving the C∧N ligands, with quantum yields of up to 0.34 in fluid solution and 0.77 in the rigid matrix at 298 K. The time-dependent density functional theory (TD-DFT) calculations reveal that nonemissive, deactivating excited states of ligand-to-metal charge-transfer (LMCT) character are pushed to high energies as a consequence of the strong σ-donating ability of the carbenic moieties, making the Pt(trz)(2) subunit an essential structural component that enables efficient emissions from the chromophoric C∧N ligands, with potential application for the development of different Pt(IV) emitters with tunable properties.
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spelling pubmed-93774192022-08-16 Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands Vivancos, Ángela Bautista, Delia González-Herrero, Pablo Inorg Chem [Image: see text] The synthesis, structure, photophysical properties, and electrochemistry of the first series of Pt(IV) tris-chelates bearing cyclometalated aryl-NHC ligands are reported. The complexes have the general formula [Pt(trz)(2)(C∧N)](+), combining two units of the cyclometalated, mesoionic aryl-NHC ligand 4-butyl-3-methyl-1-phenyl-1H-1,2,3-triazol-5-ylidene (trz) with a cyclometalated 2-arylpyridine [C∧N = 2-(2,4-difluorophenyl)pyridine (dfppy), 2-phenylpyridine (ppy), 2-(p-tolyl)pyridine (tpy), 2-(2-thienyl)pyridine (thpy), 2-(9,9-dimethylfluoren-2-yl)pyridine (flpy)], and presenting a mer arrangement or metalated aryls. They exhibit a significant photostability under UV irradiation and long-lived phosphorescence in the blue to yellow color range, arising from (3)LC excited states involving the C∧N ligands, with quantum yields of up to 0.34 in fluid solution and 0.77 in the rigid matrix at 298 K. The time-dependent density functional theory (TD-DFT) calculations reveal that nonemissive, deactivating excited states of ligand-to-metal charge-transfer (LMCT) character are pushed to high energies as a consequence of the strong σ-donating ability of the carbenic moieties, making the Pt(trz)(2) subunit an essential structural component that enables efficient emissions from the chromophoric C∧N ligands, with potential application for the development of different Pt(IV) emitters with tunable properties. American Chemical Society 2022-07-21 2022-08-01 /pmc/articles/PMC9377419/ /pubmed/35860839 http://dx.doi.org/10.1021/acs.inorgchem.2c02039 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 Vivancos, Ángela
Bautista, Delia
González-Herrero, Pablo
Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title_full Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title_fullStr Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title_full_unstemmed Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title_short Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands
title_sort phosphorescent tris-cyclometalated pt(iv) complexes with mesoionic n-heterocyclic carbene and 2-arylpyridine ligands
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9377419/
https://www.ncbi.nlm.nih.gov/pubmed/35860839
http://dx.doi.org/10.1021/acs.inorgchem.2c02039
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