Chiral Aggregates of Indan-1-ol with Secondary Alcohols and Water: Laser Spectroscopy in Supersonic Beams

One color, mass selected resonant two-photon ionization (1cR2PI) spectra of supersonically expanded bare (R)-(-)indan-1-ol (IR) and its complexes with chiral and achiral mols. (solvent) have been investigated. The excitation spectrum of bare IR has been analyzed and discussed on the basis of theor. predictions at the B3LYP/6-31G** level of theory. The excitation spectra of its diastereomeric complexes with (R)-(-)-and (S)-(+)hexan-2-ol (XR or XS, resp.) and water (W) are characterized by significant shifts of their S0 S1 band origin relative to that of bare IR. The extent and the direction of these shifts are found to depend upon the structure and the configuration of solvent and are attributed to different short-range interactions in the ground and excited [IRsolvent] complexes. In particular the [IRW]n complexes display band origins blue-shifted relative to that of bare IR, attributed to the presence of an O-H.pi. electrostatic interaction between IR and W in [IRW]n. The [IRXR] and [IRXS] equil. structures have been calcd. by a mol. dynamical (MM3) sampling and PM3 semiempirical local optimization.