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A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex
A comparative study of the electronic structure of the salen ligand in the H(2)(Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitr...
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/PMC10298361/ https://www.ncbi.nlm.nih.gov/pubmed/37373016 http://dx.doi.org/10.3390/ijms24129868 |
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author | Korusenko, Petr M. Petrova, Olga V. Vereshchagin, Anatoliy A. Katin, Konstantin P. Levin, Oleg V. Nekipelov, Sergey V. Sivkov, Danil V. Sivkov, Victor N. Vinogradov, Alexander S. |
author_facet | Korusenko, Petr M. Petrova, Olga V. Vereshchagin, Anatoliy A. Katin, Konstantin P. Levin, Oleg V. Nekipelov, Sergey V. Sivkov, Danil V. Sivkov, Victor N. Vinogradov, Alexander S. |
author_sort | Korusenko, Petr M. |
collection | PubMed |
description | A comparative study of the electronic structure of the salen ligand in the H(2)(Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitrogen), and −0.4 eV (oxygen) were observed in the 1s PE spectra of the salen ligand atoms when passing from a molecule to a complex, unambiguously indicating a substantial redistribution of the valence electron density between these atoms. It is proposed that the electron density transfer to the O atoms in [Ni(Salen)] occurred not only from the Ni atom, but also from the N and C atoms. This process seemed to be realized through the delocalized conjugated π-system of the phenol C 2p electronic states of the ligand molecule. The DFT calculations (total and partial DOS) for the valence band H(2)(Salen) and [Ni(Salen)] described well the spectral shape of the UV PE spectra of both compounds and confirmed their experimental identification. An analysis of the N and O 1s NEXAFS spectra clearly indicated that the atomic structure of the ethylenediamine and phenol fragments was retained upon passing from the free salen ligand to the nickel complex. |
format | Online Article Text |
id | pubmed-10298361 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-102983612023-06-28 A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex Korusenko, Petr M. Petrova, Olga V. Vereshchagin, Anatoliy A. Katin, Konstantin P. Levin, Oleg V. Nekipelov, Sergey V. Sivkov, Danil V. Sivkov, Victor N. Vinogradov, Alexander S. Int J Mol Sci Article A comparative study of the electronic structure of the salen ligand in the H(2)(Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitrogen), and −0.4 eV (oxygen) were observed in the 1s PE spectra of the salen ligand atoms when passing from a molecule to a complex, unambiguously indicating a substantial redistribution of the valence electron density between these atoms. It is proposed that the electron density transfer to the O atoms in [Ni(Salen)] occurred not only from the Ni atom, but also from the N and C atoms. This process seemed to be realized through the delocalized conjugated π-system of the phenol C 2p electronic states of the ligand molecule. The DFT calculations (total and partial DOS) for the valence band H(2)(Salen) and [Ni(Salen)] described well the spectral shape of the UV PE spectra of both compounds and confirmed their experimental identification. An analysis of the N and O 1s NEXAFS spectra clearly indicated that the atomic structure of the ethylenediamine and phenol fragments was retained upon passing from the free salen ligand to the nickel complex. MDPI 2023-06-07 /pmc/articles/PMC10298361/ /pubmed/37373016 http://dx.doi.org/10.3390/ijms24129868 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 Korusenko, Petr M. Petrova, Olga V. Vereshchagin, Anatoliy A. Katin, Konstantin P. Levin, Oleg V. Nekipelov, Sergey V. Sivkov, Danil V. Sivkov, Victor N. Vinogradov, Alexander S. A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title | A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title_full | A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title_fullStr | A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title_full_unstemmed | A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title_short | A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H(2)(Salen) Molecule and the [Ni(Salen)] Complex |
title_sort | comparative xps, uv pes, nexafs, and dft study of the electronic structure of the salen ligand in the h(2)(salen) molecule and the [ni(salen)] complex |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10298361/ https://www.ncbi.nlm.nih.gov/pubmed/37373016 http://dx.doi.org/10.3390/ijms24129868 |
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