Excited-state decay processes of binuclear rhodium(I) isocyanide complexes
- California Inst. of Technology, Pasadena (United States)
- Brookhaven National Lab., Upton, NY (United States)
Emission lifetimes, quantum yields, and polarized excitation spectra of Rh[sub 2]b[sub 4][sup 2+] and Rh[sub 2](TMB)[sub 4][sup 2+] (b = 1,3-diisocyanopropane; TMB = 2,5-diisocyano-2,5-dimethylhexane) have been determined. The singlet and triplet d[sigma]* [yields] p[sigma]([sup 1,3]A[sub 2u]) excited states are luminescent with radiative rates of ca. 10[sup 8] and 10[sup 4] s[sup [minus]], respectively, consistent with values obtained from Strickler-Berg calculations based on the corresponding absorption bands. Both singlet and triplet upper excited states (d[pi] [yields] p[sigma] and metal-to-metal charge transfer, E[sub u] symmetry) undergo nonradiative decay primarily to [sup 3]A[sub 2u], bypassing [sup 1]A[sub 2u], and the branching ratios for decay through several intermediate states have been estimated. The temperature dependences of the lifetimes of the [sup 1]A[sub 2u] and [sup 3]A[sub 2u] states of Rh[sub 2](TMB)[sub 4][sup 2+] are interpreted in terms of a model in which potential-surface crossings with the [sup 3]B[sub 2u] d[sigma]* [yields] d[sub x[sup 2][minus]y[sup 2]] state facilitate nonradiative decay. 26 refs., 9 figs., 3 tabs.
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 5834494
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 97:17; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
COMPLEXES
DECAY
EXCITED STATES
EMISSION SPECTRA
LUMINESCENCE
ORGANOMETALLIC COMPOUNDS
POLARIZATION
RHODIUM COMPOUNDS
ENERGY LEVELS
ORGANIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
664100 - Theory of Electronic Structure of Atoms & Molecules- (1992-)