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Synthesis of optically active through-space conjugated polymers consisting of planar chiral pseudo-meta-disubstituted [2.2]paracyclophane

Abstract

The polymerization of enantiopure pseudo-meta-diethynyl[2.2]paracyclophane with a diiodobenzene derivative was carried out through Sonogashira-Hagihara cross-coupling. The synthesized polymers consisted of three-ring para-phenylene-ethynylene π-electron systems that were stacked on each other at the terminal benzenes. The electrical photoconductivities of the pseudo-meta-linked and pseudo-para-linked polymers were examined. The corresponding optically active pseudo-meta-linked dimers were prepared, and their optical and chiroptical properties were compared with those of the pseudo-para- and pseudo-ortho-linked dimers. Optically active pseudo-meta-linked dimers and polymers emitted intense circularly polarized luminescence (CPL) with relatively high anisotropy factors on the order of 10–3. The CPL behavior of the optically active pseudo-meta-linked dimer was simulated using time-dependent density functional theory calculations.

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Acknowledgements

The authors are grateful to Professor Kazuo Tanaka and Dr. Masayuki Gon (Graduate School of Engineering, Kyoto University) for CD and CPL spectroscopy. The financial support by Grant-in-Aid for Scientific Research (B) (No. 19H02792) from the Japan Society for the Promotion of Science is acknowledged (YM). This work was also partly supported by the Nippon Sheet Glass Foundation for Materials Science and Engineering (YM).

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Maeda, H., Inoue, R., Saeki, A. et al. Synthesis of optically active through-space conjugated polymers consisting of planar chiral pseudo-meta-disubstituted [2.2]paracyclophane. Polym J (2022). https://doi.org/10.1038/s41428-022-00703-2

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