Photoinduced linkage isomers in a model ruthenium nitrosyl complex: Identification and assignment of vibrational modes
| Autor: | Theo Woike, Artem A. Mikhailov, Dominik Schaniel, Gennadiy A. Kostin, Axel Gansmüller |
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| Přispěvatelé: | Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Range (particle radiation)
Spectrophotometry Infrared Photoisomerization 010405 organic chemistry Photodissociation chemistry.chemical_element Reversible process Crystallography X-Ray Nitric Oxide 010402 general chemistry Vibration 01 natural sciences Ruthenium Atomic and Molecular Physics and Optics 0104 chemical sciences Analytical Chemistry Bond length Crystallography chemistry [CHIM.ANAL]Chemical Sciences/Analytical chemistry Molecular vibration Linkage isomerism Instrumentation Spectroscopy |
| Zdroj: | Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-...] Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-..], Elsevier, 2021, 263, pp.120217. ⟨10.1016/j.saa.2021.120217⟩ |
| ISSN: | 1386-1425 |
| Popis: | Photoinduced NO-linkage isomers were investigated in the solid state of labelled trans-[Ru(14/15NO)(py4)F](ClO4)2 complex by combined IR-spectroscopy and DFT calculations. Based on the experimental data and the DFT calculations of this isotopically labelled 14/15NO nitrosyl compound, we present a complete assignment of the vibrational bands of three nitrosyl linkage isomers in a range from 4000 to 200 cm-1. The calculated IR-spectra match well with the experimental data allowing reliable assignment of the vibrational bands. The structural change from the Ru-NO (GS) to the Ru-ON (MS1) and Ru-η2-(NO) (MS2) linkage configuration leads to the downshift of the ν(NO) and ν(Ru-(NO)) bands, and a corresponding increase of the energy of the ν(Ru-F) band. The shift of the bands corresponds to the change of the Ru-(NO) and Ru-F bond lengths: increase of the Ru-(NO) bond length leads to the decrease of the energy of the ν(Ru-(NO)) band; decrease of the Ru-F bond length leads to the increase of the energy of the ν(Ru-F) band. These observations can be extrapolated to the family of related nitrosyl complexes and therefore be used for the qualitative prediction of the Ru-(NO) and Ru-Ltrans-to-NO bond lengths of different linkage isomers in the framework of one complex. While the formation of linkage isomers is a reversible process, long-time irradiation sometimes induces irreversible reactions such as the release of NO. Here, we show that the photolysis of trans-[Ru(14/15NO)(py4)F](ClO4)2 in KBr pellets may lead to the release of nitrous oxide N2O, conceivably through the formation of a {Ru-(κ2-ONNO)} intermediate. |
| Databáze: | OpenAIRE |
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