Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study
The preparation and characterization of two novel europium–azobenzene complexes that demonstrate the effectiveness of this ligand for stabilizing reactive, redox-active metals are reported. With the family of rare earth metals receiving attention due to their potential as catalysts, critical compone...
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2024-11-01
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| author | Damian G. Allis Ana Torvisco Cody C. Webb Miriam M. Gillett-Kunnath Karin Ruhlandt-Senge |
| author_facet | Damian G. Allis Ana Torvisco Cody C. Webb Miriam M. Gillett-Kunnath Karin Ruhlandt-Senge |
| author_sort | Damian G. Allis |
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| description | The preparation and characterization of two novel europium–azobenzene complexes that demonstrate the effectiveness of this ligand for stabilizing reactive, redox-active metals are reported. With the family of rare earth metals receiving attention due to their potential as catalysts, critical components in electronic devices, and, more recently, in biomedical applications, a detailed understanding of factors contributing to their coordination chemistry is of great importance for customizing their stability and reactivity. This study introduces azobenzene as an effective nonprotic ligand system that provides novel insights into rare earth metal coordination preferences, including factors contributing to the coordinative saturation of the large, divalent europium centers. The two compounds demonstrate the impact of the solvent donors (tetrahydrofuran (THF) and dimethoxyethane (DME)) on the overall coordination chemistry of the target compounds. Apart from the side-on coordination of the doubly-reduced azobenzene and the anticipated N-N bond elongation due to decreased bond order, the two compounds demonstrate the propensity of the europium centers towards limited metal-π interactions. The target compounds are available by direct metallation in a straightforward manner with good yields and purity. The compounds demonstrate the utility of the azobenzene ligands, which may function as singly- or doubly-reduced entities in conjunction with redox-active metals. An initial exploration into the computational modeling of these and similar complexes for subsequent property prediction and optimization is performed through a methodological survey of structure reproduction using density functional theory. |
| format | Article |
| id | doaj-art-46c71b7c36e445b19d6dfb042ec07b0d |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | MDPI AG |
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| spelling | doaj-art-46c71b7c36e445b19d6dfb042ec07b0d2024-11-08T14:38:36ZengMDPI AGMolecules1420-30492024-11-012921518710.3390/molecules29215187Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical StudyDamian G. Allis0Ana Torvisco1Cody C. Webb2Miriam M. Gillett-Kunnath3Karin Ruhlandt-Senge4Department of Chemistry, Syracuse University, Syracuse, NY 13210, USAInstitute of Inorganic Chemistry, Technical University of Graz, 8010 Graz, AustriaDepartment of Chemistry, Syracuse University, Syracuse, NY 13210, USADepartment of Chemistry, Syracuse University, Syracuse, NY 13210, USADepartment for Physical & Environmental Sciences, University of Toronto, Scarborough, ON M1C 1A4, CanadaThe preparation and characterization of two novel europium–azobenzene complexes that demonstrate the effectiveness of this ligand for stabilizing reactive, redox-active metals are reported. With the family of rare earth metals receiving attention due to their potential as catalysts, critical components in electronic devices, and, more recently, in biomedical applications, a detailed understanding of factors contributing to their coordination chemistry is of great importance for customizing their stability and reactivity. This study introduces azobenzene as an effective nonprotic ligand system that provides novel insights into rare earth metal coordination preferences, including factors contributing to the coordinative saturation of the large, divalent europium centers. The two compounds demonstrate the impact of the solvent donors (tetrahydrofuran (THF) and dimethoxyethane (DME)) on the overall coordination chemistry of the target compounds. Apart from the side-on coordination of the doubly-reduced azobenzene and the anticipated N-N bond elongation due to decreased bond order, the two compounds demonstrate the propensity of the europium centers towards limited metal-π interactions. The target compounds are available by direct metallation in a straightforward manner with good yields and purity. The compounds demonstrate the utility of the azobenzene ligands, which may function as singly- or doubly-reduced entities in conjunction with redox-active metals. An initial exploration into the computational modeling of these and similar complexes for subsequent property prediction and optimization is performed through a methodological survey of structure reproduction using density functional theory.https://www.mdpi.com/1420-3049/29/21/5187europiumazobenzenecoordination chemistryeuropium-π bondingstructural characterization |
| spellingShingle | Damian G. Allis Ana Torvisco Cody C. Webb Miriam M. Gillett-Kunnath Karin Ruhlandt-Senge Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study Molecules europium azobenzene coordination chemistry europium-π bonding structural characterization |
| title | Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study |
| title_full | Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study |
| title_fullStr | Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study |
| title_full_unstemmed | Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study |
| title_short | Azobenzene as an Effective Ligand in Europium Chemistry—A Synthetic and Theoretical Study |
| title_sort | azobenzene as an effective ligand in europium chemistry a synthetic and theoretical study |
| topic | europium azobenzene coordination chemistry europium-π bonding structural characterization |
| url | https://www.mdpi.com/1420-3049/29/21/5187 |
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