TY - JOUR
T1 - Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes
AU - Tani, Keita
AU - Imafuku, Risa
AU - Miyanaga, Kanae
AU - Masaki, Miyuki Eiraku
AU - Kato, Haruka
AU - Hori, Kazushige
AU - Kubono, Koji
AU - Taneda, Masatsugu
AU - Harada, Takunori
AU - Goto, Kenta
AU - Tani, Fumito
AU - Mori, Tadashi
N1 - Funding Information:
Financial support to K.T. by Cooperative Research Program of Network Joint Research Center for Materials and Devices (Grant no. 20191331) and to T.M. by Grant-in-Aids for Scientific Research, Challenging Exploratory Research, Promotion of Joint International Research (Fostering Joint International Research), and on Innovative Areas “Photosynergetics” (Grant nos. JP16H06041, JP16KK0111, JP17H05261, JP18K19077, and JP18H01964) from JSPS, by Asahi Glass Foundation, Murata Science Foundation, Tonen General Sekiyu Research/Development Encouragement & Scholarship Foundation, and by the Cooperative Research Program of Network Joint Research Center for Materials and Devices is greatly acknowledged.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/3/12
Y1 - 2020/3/12
N2 - Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study, C2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1-CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their 1Lb and 1La transitions (|Δϵ| = 10-12 and 51-57 M-1 cm-1, respectively), while intense CEs were notified in their 1B transitions (|Δϵ| = 156-216 M-1 cm-1), absorption dissymmetry (gabs) factors being in orders of 10-2. Circularly polarized luminescence spectrum was also obtained for cyanamide derivative CZ1, with a comparative luminescence dissymmetry (glum) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivative CZ2.
AB - Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study, C2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1-CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their 1Lb and 1La transitions (|Δϵ| = 10-12 and 51-57 M-1 cm-1, respectively), while intense CEs were notified in their 1B transitions (|Δϵ| = 156-216 M-1 cm-1), absorption dissymmetry (gabs) factors being in orders of 10-2. Circularly polarized luminescence spectrum was also obtained for cyanamide derivative CZ1, with a comparative luminescence dissymmetry (glum) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivative CZ2.
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U2 - 10.1021/acs.jpca.0c00286
DO - 10.1021/acs.jpca.0c00286
M3 - Article
C2 - 32077298
AN - SCOPUS:85081944164
SN - 1089-5639
VL - 124
SP - 2057
EP - 2063
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 10
ER -