Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation
Three novel heterometallic Ni/Cd coordination compounds [Ni(en)<sub>3</sub>][CdCl<sub>4</sub>]∙3dmso (<b>1</b>), [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>][CdBr<sub>4</sub>] (<b>2</b>), and [Ni(en)<sub>3</sub>...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/22/7652 |
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| author | Oksana V. Nesterova Svitlana R. Petrusenko Brian W. Skelton Dmytro S. Nesterov |
| author_facet | Oksana V. Nesterova Svitlana R. Petrusenko Brian W. Skelton Dmytro S. Nesterov |
| author_sort | Oksana V. Nesterova |
| collection | DOAJ |
| description | Three novel heterometallic Ni/Cd coordination compounds [Ni(en)<sub>3</sub>][CdCl<sub>4</sub>]∙3dmso (<b>1</b>), [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>][CdBr<sub>4</sub>] (<b>2</b>), and [Ni(en)<sub>3</sub>]<sub>2</sub>[CdI<sub>4</sub>](I)<sub>2</sub> (<b>3</b>) have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NH<sub>4</sub>X (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for <b>1</b>) or dmf (for <b>2</b> and <b>3</b>). Formation of the one- (<b>1</b>) or three-dimensional (<b>2</b> and <b>3</b>) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX<sub>4</sub>]<sup>2−</sup> counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)<sub>3</sub>]<sup>2+</sup> and [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations. The non-covalent intermolecular contacts between the cationic nickel and anionic cadmium blocks in the solid state were investigated by the QTAIM analysis. The mechanism of ligand substitution at the nickel center in [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> was theoretically investigated at the ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP level. The results demonstrate that thermodynamic factors are structure-determining ones due to low energy barriers of the rotation of dmf ligands in [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> (below 3 kcal mol<sup>−1</sup>) and the reversible transformation of [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> into [Ni(en)<sub>3</sub>]<sup>2+</sup> (below 20 kcal mol<sup>−1</sup>). |
| first_indexed | 2024-03-09T16:34:33Z |
| format | Article |
| id | doaj.art-ab27eac8d64a4a5088f8aa185eb7ab0e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T16:34:33Z |
| publishDate | 2023-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-ab27eac8d64a4a5088f8aa185eb7ab0e2023-11-24T14:58:34ZengMDPI AGMolecules1420-30492023-11-012822765210.3390/molecules28227652Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical InvestigationOksana V. Nesterova0Svitlana R. Petrusenko1Brian W. Skelton2Dmytro S. Nesterov3Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, PortugalDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Str., 01601 Kyiv, UkraineSchool of Molecular Sciences, M310, University of Western Australia, 35 Stirling Hwy, Perth, WA 6009, AustraliaCentro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, PortugalThree novel heterometallic Ni/Cd coordination compounds [Ni(en)<sub>3</sub>][CdCl<sub>4</sub>]∙3dmso (<b>1</b>), [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>][CdBr<sub>4</sub>] (<b>2</b>), and [Ni(en)<sub>3</sub>]<sub>2</sub>[CdI<sub>4</sub>](I)<sub>2</sub> (<b>3</b>) have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NH<sub>4</sub>X (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for <b>1</b>) or dmf (for <b>2</b> and <b>3</b>). Formation of the one- (<b>1</b>) or three-dimensional (<b>2</b> and <b>3</b>) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX<sub>4</sub>]<sup>2−</sup> counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)<sub>3</sub>]<sup>2+</sup> and [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations. The non-covalent intermolecular contacts between the cationic nickel and anionic cadmium blocks in the solid state were investigated by the QTAIM analysis. The mechanism of ligand substitution at the nickel center in [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> was theoretically investigated at the ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP level. The results demonstrate that thermodynamic factors are structure-determining ones due to low energy barriers of the rotation of dmf ligands in [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> (below 3 kcal mol<sup>−1</sup>) and the reversible transformation of [Ni(en)<sub>2</sub>(dmf)<sub>2</sub>]<sup>2+</sup> into [Ni(en)<sub>3</sub>]<sup>2+</sup> (below 20 kcal mol<sup>−1</sup>).https://www.mdpi.com/1420-3049/28/22/7652nickelcadmiumheterometallic complexesethylenediamineDFT calculationsreaction mechanisms |
| spellingShingle | Oksana V. Nesterova Svitlana R. Petrusenko Brian W. Skelton Dmytro S. Nesterov Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation Molecules nickel cadmium heterometallic complexes ethylenediamine DFT calculations reaction mechanisms |
| title | Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation |
| title_full | Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation |
| title_fullStr | Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation |
| title_full_unstemmed | Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation |
| title_short | Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation |
| title_sort | halogen dependent diversity and weak interactions in the heterometallic ni cd complex solids structural and theoretical investigation |
| topic | nickel cadmium heterometallic complexes ethylenediamine DFT calculations reaction mechanisms |
| url | https://www.mdpi.com/1420-3049/28/22/7652 |
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