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UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn2+(benzo-15-crown-5)(H2O)0–2
- Source :
- The Journal of Physical Chemistry - Part A; August 2019, Vol. 123 Issue: 31 p6781-6786, 6p
- Publication Year :
- 2019
-
Abstract
- Ultraviolet photodissociation (UVPD) and IR–UV double-resonance spectroscopy are performed for bare and microhydrated complexes of Mn2+(benzo-15-crown-5), Mn2+(B15C5)(H2O)n(n= 0–2), under cold (∼10 K) gas-phase conditions. Density functional theory (DFT) calculations are also carried out to derive information on the geometric and electronic structures of the complexes from the experimental results. The n= 0 complex shows broad features in the UVPD spectrum, whereas the UV spectra of the n= 1 and 2 complexes exhibit sharp vibronic bands. The IR–UV and DFT results suggest that there is only one isomer each for the n= 1 and 2 complexes in which H2O molecules are directly attached to the Mn2+ion through Mn2+···OH2bonds with no intermolecular bond between the water molecules. Time-dependent DFT calculations suggest that the π–π* transition of the B15C5 part is highly mixed with the “ligand to metal charge transfer” transition in the n= 0 complex, which can result in broad features in the UVPD spectrum. In contrast, attachment of H2O molecules to Mn2+(B15C5) suppresses the mixing, providing sharp vibronic bands assignable to the π–π* transition for the n= 1 and 2 complexes. These results indicate that the electronic structure and transition of benzo-crown ether complexes with transition metals are strongly affected by solvation.
Details
- Language :
- English
- ISSN :
- 10895639 and 15205215
- Volume :
- 123
- Issue :
- 31
- Database :
- Supplemental Index
- Journal :
- The Journal of Physical Chemistry - Part A
- Publication Type :
- Periodical
- Accession number :
- ejs50588986
- Full Text :
- https://doi.org/10.1021/acs.jpca.9b05706