The Effect of the pi-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality
Abbreviated Journal Title
J. Phys. Chem. Lett.
ABSOLUTE STEREOCHEMISTRY; SPECTROSCOPY; ABSORPTION; EXCHANGE; DENSITY; Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, ; Multidisciplinary; Physics, Atomic, Molecular & Chemical
Herein we report on the theoretical-experimental study of the effect of curvature of the pi-electron delocalization on the two-photon circular dichroism (TPCD) of a family of optically active biaryl derivatives (S-BINOL, S-VANOL, and S-VAPOL). The comparative analysis of the influence of the different transition moments to their corresponding TPCD rotatory strength reveals an enhanced contribution of the magnetic transition dipole moment on VAPOL. This effect is hereby attributed to the additional twist in the pi-electron delocalization on this compound. TPCD measurements were done using the double L-scan technique in the picosecond regime. Theoretical calculations were completed using modern analytical response theory, within a time dependent density functional theory (TD-DFT) approach, at both, B3LYP and CAM-B3LYP levels, with the aug-cc-pVDZ basis set for S-BINOL and S-VANOL, and 6-31G* for S-VAPOL. Solvent effects were included by means of the polarizable continuum model (PCM) in CH2Cl2.
Journal of Physical Chemistry Letters
"The Effect of the pi-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality" (2012). Faculty Bibliography 2010s. 2488.