Conformational Study of an Axially Chiral Salen Ligand in Solution using Two-Photon Circular Dichroism and the Fragment-Recombination Approach

    Authors

    C. Diaz; L. Echevarria;F. E. Hernandez

    Comments

    Authors: contact us about adding a copy of your work at [email protected]

    Abbreviated Journal Title

    J. Phys. Chem. A

    Keywords

    FLUORESCENCE MICROSCOPY; AB-INITIO; ABSORPTION; DENSITY; MOLECULES; EXCHANGE; Chemistry, Physical; Physics, Atomic, Molecular & Chemical

    Abstract

    Herein we report on the conformational study of a chiral Salen ligand, AFX-155, in THF solution using two-photon absorption (TPA) and, even more importantly, two-photon circular dichroism (TPCD). The fragment-recombination approach (FRA), employed to perform computations on half-AXF-155 (AXF-169') and the center (C-AXF-155), allowed us to overcome the current computational limitations found in calculations of the TPCD spectra of large molecules. The comparative experimental theoretical analysis of AXF-155 showed that its TPA is mainly determined by AXF-169' and validated, through TPCD, the presence of the two dominant Trans_R-Intra(NHB)//Trans_R-Extra(HB) and Trans_R-Intra(NHB)//Trans_R-Extra(NHB) structure in THF with a Delta Delta propeller chirality on the diphenylamine moieties at the end of each AXF-169'. The application of FRA for the analysis of the TPCD spectra of large chiral molecules has been proven to be effective.

    Journal Title

    Journal of Physical Chemistry A

    Volume

    117

    Issue/Number

    35

    Publication Date

    1-1-2013

    Document Type

    Article

    Language

    English

    First Page

    8416

    Last Page

    8426

    WOS Identifier

    WOS:000330145200010

    ISSN

    1089-5639

    Share

    COinS
     

    Accessibility Statement

    This item was created or digitized prior to April 24, 2027, or is a reproduction of legacy media created before that date. It is preserved in its original, unmodified state specifically for research, reference, or historical recordkeeping. In accordance with the ADA Title II Final Rule, the University Libraries provides accessible versions of archival materials upon request. To request an accommodation for this item, please submit an accessibility request form.