Rs. Murphy et al., Photophysical and theoretical studies on the stereoselective complexation of naphthylethanols with beta-cyclodextrin, LANGMUIR, 16(23), 2000, pp. 8780-8788
Stereoselective binding of the l-naphthyl-l-ethanol (1-NpOH) and 2-naphthyl
-1-ethanol (2-NpOH) enantiomers with beta -cyclodextrin (beta -CD) was inve
stigated by photophysical and theoretical studies. The latter are based on
structural calculations of the complexes and their respective induced circu
lar dichroism spectra. For the enantiomers of 1-NpOH, where the complexes w
ith beta -CD have a 1:1 (guest:CD) stoichiometry, a mixture of structures w
ith different geometries was observed for each enantiomer. No stereoselecti
vity was apparent for these complexes. (R)- and (S)-2-NpOH form complexes w
ith beta -CD that have both 1:1 and 2:2 stoichiometries. Structural calcula
tions indicate that the naphthyl moiety of both enantiomers is preferential
ly included in the CD cavity for the 1:1 complex. In the case of the comple
xes with 2:2 stoichiometry, a mixture of complexes is present that either h
ave the naphthyl moieties at a distance or in close proximity. The former g
eometry explains the observation of long-lived excited triplet states for 2
-NpOH, whereas the latter geometry is responsible for the excimer emission.
The stereoselectivity observed for the monomer to excimer intensity ratios
when (R)- and (S)-2-NpOH are complexed to beta -CD is due to the different
contributions of 2:2 complexes with different geometries.