The time-resolved Raman spectra of the first triplet state–in resonance with the Tn←T1 absorption at
370 nm–and of the radical cation transient–in resonance with the R+⋅∗←R+⋅ absorptions at 370 nm and
in the 560-600 nm range-are reported for fluorene. The triplet state Raman spectra of dibenzofuran and
dibenzothiophen are also given. The vibrational assignments, resonance Raman activity and intensity
enhancement effects are studied. On this basis, the structures and electronic configurations of the triplet
state and radical cation transients and the nature of the resonant Tn←T1 and R+⋅∗←R+⋅ transitions are
discussed. It turns out from this investigation that the title molecules present close analogies with
biphenyl. The insertion of a methylene group or a heteroatom does not disturb markedly the electronic
properties of the ground state, the first triplet state and the radical cation transient of biphenyl.