TY - JOUR
T1 - Synthesis, Structure, and Photophysical/Chiroptical Properties of Benzopicene-Based π-Conjugated Molecules
AU - Murayama, Koichi
AU - Shibata, Yu
AU - Sugiyama, Haruki
AU - Uekusa, Hidehiro
AU - Tanaka, Ken
N1 - Funding Information:
This work was supported by ACT-C from JST and MEXT KAKENHI Grant Number JP 26102004. K.M. thanks JSPS research fellowship for young scientists. We thank Prof. Toshikazu Takata and Dr. Kazuko Nakazono (Tokyo Institute of Technology) for the measurement of ECD, and Prof. Keisuke Suzuki and Prof. Ken Ohmori (Tokyo Institute of Technology) for collecting the 13C NMR spectrum of 9b. We also thank Takasago International Corporation for the gift of H8−BINAP and Segphos, Umicore for generous support in supplying the rhodium and palladium complexes, and Central Glass Co., Ltd. for the gift of trifluoromethanesulfonic anhydride.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2017/1/20
Y1 - 2017/1/20
N2 - The convenient synthesis of substituted benzopicenes and azabenzopicenes has been achieved by the cationic rhodium(I)/H8-BINAP or BINAP complex-catalyzed [2+2+2] cycloaddition under mild conditions. This method was applied to the synthesis of benzopicene-based long ladder and helical molecules. The X-ray crystal structure analysis revealed that the benzopicene-based helical molecule is highly distorted and the average distance of overlapped rings is markedly shorter than that in the triphenylene-based helical molecule. Photophysical and chiroptical properties of these benzopicene and azabenzopicene derivatives have also been examined. With respect to photophysical properties, substituted benzopicenes and azabenzopicenes showed red shifts of absorption and emission maxima compared with the corresponding triphenylenes and azatriphenylenes. With respect to chiroptical properties, the CPL spectra of the benzopicene-based helical molecule showed two opposite peaks, and thus the value of the CPL was smaller than that of the triphenylene-based helical molecule presumably due to the presence of two chiral fluorophores.
AB - The convenient synthesis of substituted benzopicenes and azabenzopicenes has been achieved by the cationic rhodium(I)/H8-BINAP or BINAP complex-catalyzed [2+2+2] cycloaddition under mild conditions. This method was applied to the synthesis of benzopicene-based long ladder and helical molecules. The X-ray crystal structure analysis revealed that the benzopicene-based helical molecule is highly distorted and the average distance of overlapped rings is markedly shorter than that in the triphenylene-based helical molecule. Photophysical and chiroptical properties of these benzopicene and azabenzopicene derivatives have also been examined. With respect to photophysical properties, substituted benzopicenes and azabenzopicenes showed red shifts of absorption and emission maxima compared with the corresponding triphenylenes and azatriphenylenes. With respect to chiroptical properties, the CPL spectra of the benzopicene-based helical molecule showed two opposite peaks, and thus the value of the CPL was smaller than that of the triphenylene-based helical molecule presumably due to the presence of two chiral fluorophores.
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U2 - 10.1021/acs.joc.6b02757
DO - 10.1021/acs.joc.6b02757
M3 - Article
C2 - 28035821
AN - SCOPUS:85042108249
SN - 0022-3263
VL - 82
SP - 1136
EP - 1144
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 2
ER -