RESUMEN
We present aspects of emerging optical activity in thin racemic 1,1'-Bi-2-naphthol films upon irradiation with circularly polarized light and subsequent resonant two-photon absorption in the sample. Thorough analysis of the sample morphology is conducted by means of (polarization-resolved) optical microscopy and scanning electron microscopy (SEM). The influence of crystallization on the nonlinear probing technique (second harmonic generation circular dichroism [SHG-CD]) is investigated. Optical activity and crystallization are brought together by a systematic investigation in different crystallization regimes. We find crystallization to be responsible for two counter-acting effects, which arise for different states of crystallization. Measuring crystallized samples offers the best signal-to-noise ratio, but it limits generation of optical activity due to self-assembly effects. For suppression of crystallization on the other hand, there is a clear indication that enantiomeric selective desorption is responsible for the generation of optical activity in the sample. We reach the current resolution limit of probing with SHG-CD, as we suppress the crystallization in the racemic sample during desorption. In addition, intensity-dependent measurements on the induced optical activity reveal an onset threshold (≈0.7 TW cm-2), above which higher order nonlinear processes impair the generation of optical activity by desorption with CPL.
RESUMEN
The interest in enantioseparation and enantiopurification of chiral molecules has been drastically increasing over the past decades, since these are important steps in various disciplines such as pharmaceutical industry, asymmetric catalysis, and chiral sensing. By exposing racemic samples of BINOL (1,1'-bi-2-naphthol) coated onto achiral glass substrates to circularly polarized light, we unambiguously demonstrate that by controlling the handedness of circularly polarized light, preferential desorption of enantiomers can be achieved. There are currently no mechanisms known that would describe this phenomenon. Our observation together with a simplified phenomenological model suggests that the process of laser desorption needs to be further developed and the contribution of quantum mechanical processes should be revisited to account for these data. Asymmetric laser desorption provides us with a contamination-free technique for the enantioenrichment of chiral compounds.
RESUMEN
Using density functional theory and its time-dependent extension for excited states, the S0 âS1 high-resolution vibronic absorption and electronic circular dichroism spectra of (R)-(+)-1-phenylethanol are computed and compared to experimental spectra measured in jet-cooled conditions in the region within 1000â cm-1 of the 0-0 transition. The agreement between theory and computation is satisfactory and allows a confident assignment of several experimental bands in terms of fundamentals of different modes. Cases are documented for which the analysis of optical anisotropy factors, owing to their signed nature, remarkably enhances the possibility of a robust assignment of the experimental absorption bands. Computational analysis shows that the experimental spectra are dominated by Herzberg-Teller contributions and that the electronic circular dichroism spectrum and the anisotropy factors are also strongly modulated by the effect of Duschinsky mixings.
RESUMEN
Circular dichroism-resonance-enhanced multiphoton ionization (CD-REMPI) was used for CD measurements on several single vibronic transitions of supersonic beam-cooled (R)-(+)-1-phenylethanol. Due to the low molecular densities within a supersonic beam and the expected small anisotropy factor of 1-phenylethanol in the permille region, the precision of the experimental method had to be significantly improved. Therefore, a single laser pulse evaluation combined with a twin-peak technique enabled within the used supersonic beam setup is presented. For the electronic transition S0 â S1 of (R)-(+)-1-phenylethanol (π â π* transition of the phenyl ring at 266 nm) ten different vibrational modes as well as the 0-transition were investigated with one-color (1 + 1) CD-REMPI. The results deliver new experimental insights on the influence of molecular vibrations on the anisotropy factor. TD-DFT theoretical predictions show how the angle between the electronic and magnetic transition dipole moments of the electronic transition can be modified by different vibrational modes, making even a flip of the sign of the anisotropy factor possible.