Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes

Vincent M. Miskowski, Glenn L. Nobinger, David S. Kliger, George S. Hammond, Nathan S Lewis, Kent R. Mann, Harry B. Gray

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Abstract

Excitation of concentrated acetonitrile solutions of [Rh(tol)4]PF6 (tol is p-methylphenyl isocyanide) at 562 nm, where strong absorption attributable to [Rh2(tol)8]2+ occurs, produces emission (λmax 697 nm) with a quantum yield of 0.0065 and a lifetime of ≤2 ns. Excitation of [Rh2(bridge)4](BPh4)2 (bridge is 1,3-diisocyanopropane) in acetonitrile solution at 553 nm gives emission at 656 nm with a quantum yield of 0.056 and a lifetime of ≤2 ns. The emission is assigned to 1A2u1A1g (2a1g → 1a2u) in both dinuclear Rh(I) complexes. Excitation also gives rise to long-lived transient absorptions attributable to the following dinuclear and trinuclear species: ∼8 μs, Rh2(bridge)42+; 0.09 μs, [Rh2(tol)8]2+; and 0.14 μs, [Rh3(tol)12]3+. In the dinuclear complexes, this transient is most likely 3A2u, which is the triplet excited-state partner of 1A2u. The results suggest that the spin-orbit components of 3A2u possess very little singlet character.

Original languageEnglish
Pages (from-to)485-488
Number of pages4
JournalJournal of the American Chemical Society
Volume100
Issue number2
Publication statusPublished - 1978

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Rhodium
Quantum yield
Acetonitrile
Kinetics
Cyanides
Orbit
Excited states
Orbits
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Miskowski, V. M., Nobinger, G. L., Kliger, D. S., Hammond, G. S., Lewis, N. S., Mann, K. R., & Gray, H. B. (1978). Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes. Journal of the American Chemical Society, 100(2), 485-488.

Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes. / Miskowski, Vincent M.; Nobinger, Glenn L.; Kliger, David S.; Hammond, George S.; Lewis, Nathan S; Mann, Kent R.; Gray, Harry B.

In: Journal of the American Chemical Society, Vol. 100, No. 2, 1978, p. 485-488.

Research output: Contribution to journalArticle

Miskowski, VM, Nobinger, GL, Kliger, DS, Hammond, GS, Lewis, NS, Mann, KR & Gray, HB 1978, 'Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes', Journal of the American Chemical Society, vol. 100, no. 2, pp. 485-488.
Miskowski VM, Nobinger GL, Kliger DS, Hammond GS, Lewis NS, Mann KR et al. Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes. Journal of the American Chemical Society. 1978;100(2):485-488.
Miskowski, Vincent M. ; Nobinger, Glenn L. ; Kliger, David S. ; Hammond, George S. ; Lewis, Nathan S ; Mann, Kent R. ; Gray, Harry B. / Flash kinetic spectroscopic studies of dinuclear rhodium(I) complexes. In: Journal of the American Chemical Society. 1978 ; Vol. 100, No. 2. pp. 485-488.
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