Phosphorescence and zero-field optically detected magnetic resonance studies of (nd){sup 10} transition-metal complexes. 1. ZnX{sub 2}(phen) (X = Cl, Br, I)
- Tohoku Univ., Sendai (Japan); and others
In order to elucidate the effect of (nd){sup 10} central metal ions on the properties of the low-lying excited states of metal complexes, spectroscopic and optically detected magnetic resonance studies on the phenanthroline (phen) localized {sup 3}{pi}{pi}* states of ZnX{sub 2}(phen) (X = Cl, Br, I) were carried out. Comparison of the properties of the spin sublevels of ZnX{sub 2}(phen) with those of the uncoordinated 1, 10-phenanthroline yielded several noteworthy features: (a) the phosphorescence spectra of ZnX{sub 2}(phen) complexes very closely resemble that of the uncoordinated phen molecule, (b) the magnitudes of the zero-field splittings follow the ordering phen > ZnCl{sub 2}(phen) replacing the z sublevel (in-plane component) as the dominant decay channel in uncoordinated phen. These experimental results have been interpreted systematically and satisfactorily by a model invoking Heitler-London type mixing of LLCT (halogen p-orbitals to phen charge transfer) electronic configurations with the phen locally excited electronic configuration. 31 refs., 4 figs., 7 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG06-87ER13809
- OSTI ID:
- 468064
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 16 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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