The Effect of the pi-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality

    Authors

    C. Diaz; N. Lin; C. Toro; R. Passier; A. Rizzo;F. E. Hernandez

    Comments

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    Abbreviated Journal Title

    J. Phys. Chem. Lett.

    Keywords

    ABSOLUTE STEREOCHEMISTRY; SPECTROSCOPY; ABSORPTION; EXCHANGE; DENSITY; Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, ; Multidisciplinary; Physics, Atomic, Molecular & Chemical

    Abstract

    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 Title

    Journal of Physical Chemistry Letters

    Volume

    3

    Issue/Number

    13

    Publication Date

    1-1-2012

    Document Type

    Article

    Language

    English

    First Page

    1808

    Last Page

    1813

    WOS Identifier

    WOS:000306251900015

    ISSN

    1948-7185

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