Rotational coherence spectroscopy ~RCS!, via time-correlated single photon counting, and two-color resonant two-photon ionization ~R2PI! time-of-flight mass spectrometry, have been used to characterize fluorene–(water)1,2[FL– (H2O)1,2] van der Waals clusters generated in supersonic jets. Rotational coherence traces have been obtained at excitation energies corresponding to several resonant features in the S1\u3c-S0 R2PI spectra of FL– (H2O)1,2 . RCS simulations and diagonalization of the moment of inertia tensor have been used to obtain S1 excited state rotational constants and structures of FL– (H2O)1,2 that are consistent with the experimental rotational coherence traces. The RCS results indicate that: (i) the water molecule in FL–H2O resides above the central five member ring and interacts with both aromatic sites; (ii) the water molecules in FL– (H2O)2 form a water dimer that is most likely oriented along the long axis of fluorene and is hydrogen-bonded to both aromatic sites. The S1\u3c-S0 R2PI spectra of FL– (D2O)1,2 and FL–HDO have also been obtained. The 000 transition is a doublet in the R2PI spectra of FL–H2O, FL–D2O, and a singlet in the R2PI spectrum of FL–HDO. The presence of this doublet in the FL–H2O/D2O spectra, and the absence of such a splitting in the FL–HDO spectrum, is an indication of internal rotation of the water molecule on a potential energy surface that changes upon electronic excitation. Lastly, the use of RCS and time-resolved fluorescence as a tool for assigning features in R2PI spectra that are of ambiguous origin due to fragmentation of higher mass clusters into lower mass channels is demonstrated
