Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes
For the first time, an extensive theoretical comparative study of the electronic structure and spectra of the <i>η</i><sup>5</sup>-cyclopentadienyl half-sandwich [(Cp)(EPh<sub>3</sub>)], E = Se, Te) organochalcogenides was carried out using direct space electronic...
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MDPI AG
2023-06-01
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| author | G. T. Oyeniyi Iu. A. Melchakova S. P. Polyutov P. V. Avramov |
| author_facet | G. T. Oyeniyi Iu. A. Melchakova S. P. Polyutov P. V. Avramov |
| author_sort | G. T. Oyeniyi |
| collection | DOAJ |
| description | For the first time, an extensive theoretical comparative study of the electronic structure and spectra of the <i>η</i><sup>5</sup>-cyclopentadienyl half-sandwich [(Cp)(EPh<sub>3</sub>)], E = Se, Te) organochalcogenides was carried out using direct space electronic structure calculations within hybrid, meta, and meta-hybrid DFT GGA functionals coupled with double-ζ polarized 6-31G* and correlation-consistent triple-zeta cc-pVTZ-pp basis sets. The absence of covalent bonding between the cyclopentadienyl (Cp) ligands and Te/Se coordination centers was revealed. It was found that the chalcogens are partially positively charged and Cp ligands are partially negatively charged, which directly indicates a visible ionic contribution to Te/Se-Cp chemical bonding. Simulated UV–Vis absorption spectra show that all complexes have a UV-active nature, with a considerable shift in their visible light absorption due to the addition of methyl groups. The highest occupied molecular orbitals exhibit π-bonding between the Te/Se centers and Cp rings, although the majority of the orbital density is localized inside the Cp π-system. The presence of the chalcogen atoms and the extension of π-bonds across the chalcogen-ligand interface make the species promising for advanced photovoltaic and light-emitting applications. |
| first_indexed | 2024-03-11T02:31:31Z |
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| institution | Directory Open Access Journal |
| issn | 2079-9292 |
| language | English |
| last_indexed | 2024-03-11T02:31:31Z |
| publishDate | 2023-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Electronics |
| spelling | doaj.art-380d67d2e5d64578adc0dd99e42cc03c2023-11-18T10:09:53ZengMDPI AGElectronics2079-92922023-06-011212273810.3390/electronics12122738Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide ComplexesG. T. Oyeniyi0Iu. A. Melchakova1S. P. Polyutov2P. V. Avramov3Department of Chemistry, Kyungpook National University, 80 Daehak-ro, Daegu 41566, Republic of KoreaSchool of Physics and Engineering, ITMO University, St. Petersburg 197101, RussiaInternational Research Center of Spectroscopy and Quantum Chemistry (IRC SQC), Siberian Federal University, Svobodniy pr. 79/10, 600041 Krasnoyarsk, RussiaDepartment of Chemistry, Kyungpook National University, 80 Daehak-ro, Daegu 41566, Republic of KoreaFor the first time, an extensive theoretical comparative study of the electronic structure and spectra of the <i>η</i><sup>5</sup>-cyclopentadienyl half-sandwich [(Cp)(EPh<sub>3</sub>)], E = Se, Te) organochalcogenides was carried out using direct space electronic structure calculations within hybrid, meta, and meta-hybrid DFT GGA functionals coupled with double-ζ polarized 6-31G* and correlation-consistent triple-zeta cc-pVTZ-pp basis sets. The absence of covalent bonding between the cyclopentadienyl (Cp) ligands and Te/Se coordination centers was revealed. It was found that the chalcogens are partially positively charged and Cp ligands are partially negatively charged, which directly indicates a visible ionic contribution to Te/Se-Cp chemical bonding. Simulated UV–Vis absorption spectra show that all complexes have a UV-active nature, with a considerable shift in their visible light absorption due to the addition of methyl groups. The highest occupied molecular orbitals exhibit π-bonding between the Te/Se centers and Cp rings, although the majority of the orbital density is localized inside the Cp π-system. The presence of the chalcogen atoms and the extension of π-bonds across the chalcogen-ligand interface make the species promising for advanced photovoltaic and light-emitting applications.https://www.mdpi.com/2079-9292/12/12/2738theoretical chemistryDFTTD-DFTUV–Visspectrumcoordination |
| spellingShingle | G. T. Oyeniyi Iu. A. Melchakova S. P. Polyutov P. V. Avramov Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes Electronics theoretical chemistry DFT TD-DFT UV–Vis spectrum coordination |
| title | Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes |
| title_full | Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes |
| title_fullStr | Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes |
| title_full_unstemmed | Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes |
| title_short | Theoretical DFT Investigation of Structure and Electronic Properties of <i>η</i><sup>5</sup>-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes |
| title_sort | theoretical dft investigation of structure and electronic properties of i η i sup 5 sup cyclopentadienyl half sandwich organochalcogenide complexes |
| topic | theoretical chemistry DFT TD-DFT UV–Vis spectrum coordination |
| url | https://www.mdpi.com/2079-9292/12/12/2738 |
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