TY - JOUR
T1 - Optical Activity Anisotropy of Benzil
AU - Nakagawa, Kenta
AU - Martin, Alexander T.
AU - Nichols, Shane M.
AU - Murphy, Veronica L.
AU - Kahr, Bart
AU - Asahi, Toru
N1 - Funding Information:
We thank Professor M. D. Ward for the use of his AFM and Dr. J. Yang for his assistance. This work was supported in the USA by the National Institutes of Health (5R21GM107774-02), the National Science Foundation (DMR-1105000), an NSF Predoctoral Fellowship to SMN (DGE-12342536), a Margaret Strauss Kramer Fellowship, and a Margaret and Herman Sokol Fellowship from the NYU Department of Chemistry to ATM. The Japanese contributions to this study were financially supported by the High-Tech Research Center (TWIns), the Consolidated Research Institute for Advanced Science and Medical Care (ASMeW), the Global COE for Practical Chemical Wisdom, the Leading Graduate Program in Science and Engineering, The Global University Project, Waseda University, from the Ministry of Education, Culture, Sports, Science and Technology, Japan and the grant-in-aid from the Mitsubishi Materials Corporation (Tokyo, Japan).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/11/16
Y1 - 2017/11/16
N2 - Optical activity (OA) along the optic axis of crystalline benzil has been measured by many over the past 150 years. However, the OA anisotropy remains uncharacterized due to difficulties in sample preparation as well as competition with linear birefringence (LB). The challenges associated with measuring OA along low-symmetry directions in crystals have too often left scientists with only average values of nonresonant OA in solution, i.e., specific rotations, which continue to resist interpretation in terms of structure. Measuring OA anisotropy has been facilitated by recent advances in polarimetry and optical modeling and here we compare results from two distinct division-of-time polarimeters. The absolute structure of crystalline benzil was established for the first time. The optical rotation (OR) of (+)-crystalline benzil (space group P3121) perpendicular to the optic axis at the sodium D-line is -24.6 ± 1.1°/mm. A spectroscopic optical model in the transparent region of the crystal is provided. Electronic structure calculations of OR inform the polarimetric measurements and point to the necessity of developing linear response theory with periodic boundary conditions in order to interpret the results of chiroptical measurements in crystals.
AB - Optical activity (OA) along the optic axis of crystalline benzil has been measured by many over the past 150 years. However, the OA anisotropy remains uncharacterized due to difficulties in sample preparation as well as competition with linear birefringence (LB). The challenges associated with measuring OA along low-symmetry directions in crystals have too often left scientists with only average values of nonresonant OA in solution, i.e., specific rotations, which continue to resist interpretation in terms of structure. Measuring OA anisotropy has been facilitated by recent advances in polarimetry and optical modeling and here we compare results from two distinct division-of-time polarimeters. The absolute structure of crystalline benzil was established for the first time. The optical rotation (OR) of (+)-crystalline benzil (space group P3121) perpendicular to the optic axis at the sodium D-line is -24.6 ± 1.1°/mm. A spectroscopic optical model in the transparent region of the crystal is provided. Electronic structure calculations of OR inform the polarimetric measurements and point to the necessity of developing linear response theory with periodic boundary conditions in order to interpret the results of chiroptical measurements in crystals.
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U2 - 10.1021/acs.jpcc.7b08831
DO - 10.1021/acs.jpcc.7b08831
M3 - Article
AN - SCOPUS:85034647633
SN - 1932-7447
VL - 121
SP - 25494
EP - 25502
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 45
ER -