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Significantly Stokes-shifted fluorescence induced by the UV photoexcitation of 2,2′-bipyridin-3-ol in 3-methylpentane exhibits a dramatic temperature dependence such that dual fluorescence spectra (λ max ) 560 and 585 nm) at room temperature are replaced by a single fluorescence spectrum (λ max ) 560 nm) below 200 K. The respective emitting species responsible for the short-and long-wavelength bands may be ascribed to the excited-state primary phototautomer (S 1 ′) and its rotamer (S 1 ′′), which is generated by the rotational isomerization of S 1 ′ with an activation barrier.

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