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Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes
A series of bis-metalated phosphorescent [(N^C)(2)Ir(bipyridine)](+) complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography....
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10054739/ https://www.ncbi.nlm.nih.gov/pubmed/36985710 http://dx.doi.org/10.3390/molecules28062740 |
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author | Hendi, Zohreh Kozina, Daria O. Porsev, Vitaly V. Kisel, Kristina S. Shakirova, Julia R. Tunik, Sergey P. |
author_facet | Hendi, Zohreh Kozina, Daria O. Porsev, Vitaly V. Kisel, Kristina S. Shakirova, Julia R. Tunik, Sergey P. |
author_sort | Hendi, Zohreh |
collection | PubMed |
description | A series of bis-metalated phosphorescent [(N^C)(2)Ir(bipyridine)](+) complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes’ spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the (3)LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N- and C-coordinated moieties of the N^C chelate. This hypothesis is completely in line with the trends observed in the experimental absorption and emission spectra, which display systematic bathochromic shifts upon insertion of electron-withdrawing substituents into the N-coordinated fragment. An analogous shift is induced by expansion of the aromatic system of the C-coordinated fragment and insertion of polarizable sulfur atoms into the aromatic rings. These experimental and theoretical findings extend the knowledge of the nature of photophysical processes in complexes of this type and provide useful instruments for fine-tuning of their emissive characteristics. |
format | Online Article Text |
id | pubmed-10054739 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-100547392023-03-30 Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes Hendi, Zohreh Kozina, Daria O. Porsev, Vitaly V. Kisel, Kristina S. Shakirova, Julia R. Tunik, Sergey P. Molecules Article A series of bis-metalated phosphorescent [(N^C)(2)Ir(bipyridine)](+) complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes’ spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the (3)LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N- and C-coordinated moieties of the N^C chelate. This hypothesis is completely in line with the trends observed in the experimental absorption and emission spectra, which display systematic bathochromic shifts upon insertion of electron-withdrawing substituents into the N-coordinated fragment. An analogous shift is induced by expansion of the aromatic system of the C-coordinated fragment and insertion of polarizable sulfur atoms into the aromatic rings. These experimental and theoretical findings extend the knowledge of the nature of photophysical processes in complexes of this type and provide useful instruments for fine-tuning of their emissive characteristics. MDPI 2023-03-17 /pmc/articles/PMC10054739/ /pubmed/36985710 http://dx.doi.org/10.3390/molecules28062740 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Hendi, Zohreh Kozina, Daria O. Porsev, Vitaly V. Kisel, Kristina S. Shakirova, Julia R. Tunik, Sergey P. Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title | Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title_full | Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title_fullStr | Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title_full_unstemmed | Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title_short | Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)(2)(N^N)](+) Complexes |
title_sort | investigation of the n^c ligand effects on emission characteristics in a series of bis-metalated [ir(n^c)(2)(n^n)](+) complexes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10054739/ https://www.ncbi.nlm.nih.gov/pubmed/36985710 http://dx.doi.org/10.3390/molecules28062740 |
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