Photophysics of Tungsten and Molybdenum Arylcarbyne Complexes. Observation of the Lowest Excited State by Laser Flash Photolysis
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Abstract
The photophysics of the series of tungsten and molybdenum arylcarbyne complexes Cp(CO){P(OMe)3}M⋮CAr (1a, M = W, Ar = phenyl; 1b, M = Mo, Ar = phenyl; 1c, M = W, Ar = o-tolyl; 1d, M = W, Ar = 2-naphthyl) has been examined by using absorption, emission, and transient absorption spectroscopy. Extended Hückel calculations indicate that the lowest excited state of these arylcarbyne complexes is based on a d(M) → π*(M⋮CAr) configuration. Consistent with this prediction, each of the complexes displays a weak, mid-visible absorption band which is attributed to the d → π* transition. The tungsten complexes 1a, 1c, and 1d also exhibit red luminescence with a lifetime in the 100−200 ns regime. Nanosecond laser flash photolysis studies indicate that the arylcarbyne complexes display a strong transient absorption with a maximum in the 400−450 nm region. Close correspondence between decay lifetimes obtained by luminescence and transient absorption indicate that the transient absorption may be assigned to the d → π* excited state.
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