Transient spectroscopy of the lowest excited states of binuclear rhodium(I) isocyanides

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The binuclear complexes Rh2b42+ (b = 1,3-diisocyanopropane) and Rh2(TMB)42+ (TMB = 2,5-dimethyl-2,5-diisocyanohexane) both exhibit absorption from their lowest excited singlet state (1A2u) and their lowest triplet state (3A2u). The excited-triplet-state absorption spectra are similar for the two complexes, with strong bands at 420 and 470 nm in Rh2b42+ and at 400 and 490 nm in Rh2(TMB)42+. The two bands are oppositely polarized (x-y, 420 and 400 nm; z, 470 and 490 nm) and are assigned to dπ → pσ (1eu → 2a1g) and dσ → dσ* (1a1g → 1a2u) transitions, respectively. Both complexes have weak, structureless absorptions in the red (λ > 600 nm) that are attributed to pσ → dδ (2a1g → dx2-y2) transitions. The excited singlet spectrum of each complex exhibits a strong band in the blue (450 nm, Rh2b42+; 440 nm, Rh2(TMB)42+) that is primarily z-polarized in Rh2(TMB)42+ and is assigned to dσ* → pσ (1a2u → 2a1g). © 1986 American Chemical Society.

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Journal of Physical Chemistry

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