TY - JOUR
T1 - Conformational Dynamics of Monomer- versus Dimer-like Features in a Naphthalenediimide-Based Conjugated Cyclophane
AU - Keshri, Sudhir Kumar
AU - Takai, Atsuro
AU - Ishizuka, Tomoya
AU - Kojima, Takahiko
AU - Takeuchi, Masayuki
N1 - Funding Information:
We are grateful to Dr. T. Nakanishi for using a workstation equipped with Gaussian software. We thank JASCO Co. for the measurements of CPL. This research was supported by KAKENHI, a Grant‐in‐Aid for Innovative Areas “π‐System Figuration” (No. 26102009 for M.T.) from JSPS, and the MEXT “NIMS Molecule and Material Synthesis Platform” program. S.K.K. acknowledges NIMS for offering NIMS postdoctoral fellowship.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/3/23
Y1 - 2020/3/23
N2 - The design and synthesis of an enantiomeric pair of 1,8-diethynylanthracene-bridged naphthalenediimide (NDI)-based cyclophanes (Cyclo-NDIs) are reported. Each enantiomer of Cyclo-NDI exhibits a circularly polarized luminescence signal with a relatively large luminescence dissymmetry factor (glum=±8×10−3). We have further investigated the modulation of through-space electronic communication between co-facially oriented NDIs in a discrete Cyclo-NDI with changes in the temperature. Tuning of the electronic communication results from the conformational transformation of monomer- versus dimer-like features of Cyclo-NDI, as confirmed by UV/Vis, fluorescence, circular dichroic, and NMR spectroscopic analysis. The temperature-dependent optical response in the Cyclo-NDI through the conformational transformation could be utilized as a highly sensitive and reversible optical thermometer in a wide temperature range (100 to −80 °C).
AB - The design and synthesis of an enantiomeric pair of 1,8-diethynylanthracene-bridged naphthalenediimide (NDI)-based cyclophanes (Cyclo-NDIs) are reported. Each enantiomer of Cyclo-NDI exhibits a circularly polarized luminescence signal with a relatively large luminescence dissymmetry factor (glum=±8×10−3). We have further investigated the modulation of through-space electronic communication between co-facially oriented NDIs in a discrete Cyclo-NDI with changes in the temperature. Tuning of the electronic communication results from the conformational transformation of monomer- versus dimer-like features of Cyclo-NDI, as confirmed by UV/Vis, fluorescence, circular dichroic, and NMR spectroscopic analysis. The temperature-dependent optical response in the Cyclo-NDI through the conformational transformation could be utilized as a highly sensitive and reversible optical thermometer in a wide temperature range (100 to −80 °C).
KW - circularly polarized luminescence
KW - conformational transformations
KW - cyclophanes
KW - naphthalenediimide dimers
KW - optical thermometry
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U2 - 10.1002/anie.201914414
DO - 10.1002/anie.201914414
M3 - Article
C2 - 31854072
AN - SCOPUS:85078945270
SN - 1433-7851
VL - 59
SP - 5254
EP - 5258
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 13
ER -