TY - JOUR
T1 - Circularly Polarized Luminescence Liquids Based on Siloxybinaphthyls
T2 - Best Binaphthyl Dihedral Angle in the Excited State
AU - Takaishi, Kazuto
AU - Matsumoto, Tomoki
AU - Kawataka, Miyu
AU - Ema, Tadashi
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant No. JP17K05786, the JGC‐Scholarship Foundation, and the Foundation, Oil&Fat Industry Kaikan. The computations were performed using RCCS, Okazaki, Japan. This work was partly supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of MEXT Grant No. JPMXP09S20NU0025.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/4/26
Y1 - 2021/4/26
N2 - A series of axially chiral 1,1′-binaphthyls with trialkylsiloxy (OSiR3) groups were synthesized. Among them, 1 a–c possessing OSiR3 groups at the 7,7′-positions and methyl groups at the 2,2′-positions were liquids at room temperature, and the neat liquids showed circularly polarized luminescence (CPL) (R=Bu; Φfl,liquid=0.21, |glum,liquid|=1.6×10−3). The |glum,liquid| value is the highest of pure liquids. These compounds remained liquid over a broad range of temperatures, down to −50 °C. Time-dependent DFT calculations indicated that in the excited state, the binaphthyls adopt a transoid conformation with a small angle between the electric and magnetic transition dipole moments (θμ,m=77°), which is a key factor in their CPL activity. The best binaphthyl dihedral angle in the excited state is approximately 110°.
AB - A series of axially chiral 1,1′-binaphthyls with trialkylsiloxy (OSiR3) groups were synthesized. Among them, 1 a–c possessing OSiR3 groups at the 7,7′-positions and methyl groups at the 2,2′-positions were liquids at room temperature, and the neat liquids showed circularly polarized luminescence (CPL) (R=Bu; Φfl,liquid=0.21, |glum,liquid|=1.6×10−3). The |glum,liquid| value is the highest of pure liquids. These compounds remained liquid over a broad range of temperatures, down to −50 °C. Time-dependent DFT calculations indicated that in the excited state, the binaphthyls adopt a transoid conformation with a small angle between the electric and magnetic transition dipole moments (θμ,m=77°), which is a key factor in their CPL activity. The best binaphthyl dihedral angle in the excited state is approximately 110°.
KW - binaphthyls
KW - circularly polarized luminescence
KW - conformation analysis
KW - fluorescence
KW - liquids
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U2 - 10.1002/anie.202101226
DO - 10.1002/anie.202101226
M3 - Article
C2 - 33617100
AN - SCOPUS:85103303007
SN - 1433-7851
VL - 60
SP - 9968
EP - 9972
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 18
ER -