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| Verfasst von: | Gerhards, Luca [VerfasserIn]  |
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| | Werr, Marco [VerfasserIn] |
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| | Hübner, Olaf [VerfasserIn] |
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| | Solov’yov, Ilia A. [VerfasserIn] |
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| | Himmel, Hans-Jörg [VerfasserIn] |
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| Titel: | Peculiar differences between two copper complexes containing similar redox-active ligands |
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| Titelzusatz: | density functional and multiconfigurational calculations |
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| Verf.angabe: | Luca Gerhards, Marco Werr, Olaf Hübner, Ilia A. Solov’yov, and Hans-Jörg Himmel |
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| E-Jahr: | 2024 |
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| Jahr: | 15 January 2024 |
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| Umfang: | 15 S. |
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| Illustrationen: | Illustrationen |
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| Fussnoten: | Online verfügbar: 29. Dezember 2023 ; Gesehen am 21.02.2024 |
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| Titel Quelle: | Enthalten in: Inorganic chemistry |
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| Ort Quelle: | Washington, DC : American Chemical Society, 1962 |
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| Jahr Quelle: | 2024 |
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| Band/Heft Quelle: | 63(2024), 2, Seite 961-975 |
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| ISSN Quelle: | 1520-510X |
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| Abstract: | Transition metal complexes featuring redox-active ligands often exhibit multiple redox states, influenced by the interplay between the metal center and the ligand. This study delves into the electronic structures of two mononuclear complexes of copper with two similar redox-active urea azine ligands. The ligands differ by the replacement of an NCH3 moiety by an S atom in the ligand backbone. Experimental analysis yields pronounced electronic structural disparities between these complexes, observable in both the solution and solid phases. Conventional quantum chemical methods, such as density functional theory using different functionals (B3LYP, TPSSh, and CAM-B3LYP), remain inadequate to rationalize the observed spectroscopic anomalies. However, a multiconfigurational approach elucidates the disparate behaviors of these complexes. Multireference perturbation theory, based on complete active space self-consistent field computations, identifies Cu(I) in the case of the complex with the NCH3 containing ligands and a state with substantial Cu(II) contributions in the case of the complex with the S atom containing ligands. In contrast, DFT indicates Cu(I) in both scenarios. |
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| DOI: | doi:10.1021/acs.inorgchem.3c02949 |
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| URL: | Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.
kostenfrei: Volltext: https://doi.org/10.1021/acs.inorgchem.3c02949 |
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| | kostenfrei: Volltext: https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02949 |
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| | DOI: https://doi.org/10.1021/acs.inorgchem.3c02949 |
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| Datenträger: | Online-Ressource |
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| Sprache: | eng |
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| K10plus-PPN: | 1881365301 |
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| Verknüpfungen: | → Zeitschrift |
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Peculiar differences between two copper complexes containing similar redox-active ligands / Gerhards, Luca [VerfasserIn]; 15 January 2024 (Online-Ressource)
