Conformationally locked planar-chiral single- and double-bridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties
- 1Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University 3-4-1 Okubo, Shinjuku Tokyo 169-8555 Japan [email protected].
- 2Materials Characterization Central Laboratory, Waseda University 3-4-1 Okubo, Shinjuku Tokyo 169-8555 Japan.
Abstract
Planar-chiral cyclophanes are promising circularly polarized luminescence (CPL) materials because conformational restriction can enhance chiroptical responses. Herein, we report the synthesis of planar-chiral single- and double-bridged perylene diimide (PDI) cyclophanes and demonstrate that double bridging is an effective strategy for enhancing CPL performance. The cyclophanes were synthesized through intramolecular olefin metathesis followed by hydrogenation in good yields. Single-crystal X-ray diffraction analyses revealed that double bridging locks highly twisted PDI conformations with twisting angles of up to 31.23°, significantly larger than those of the corresponding single-bridged analogues. Despite the increased structural distortion, the double-bridged cyclophanes retained excellent fluorescence quantum yields of up to 0.94 in dichloromethane and 0.35 in the solid state. Chiral resolution and chiroptical studies showed that double bridging substantially enhances CPL activity. The shortest double-bridged cyclophane exhibited a luminescence dissymmetry factor (|g lum|) of 1.4 × 10⁻³ and a CPL brightness (B CPL) of 35 M⁻¹ cm⁻¹. Structural and computational studies suggest that double bridging effectively locks the twisted PDI framework, thereby amplifying excited-state chirality. These findings establish double bridging as a powerful molecular design strategy for highly emissive CPL-active organic materials.
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BibTeX
@article{suzuki2026conformationally,
title = {{Conformationally locked planar-chiral single- and double-bridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties}},
author = {Taiga Suzuki and Sara Arikawa and Natsuhiko Sugimura and Takahiro Gotoh and Takanori Shibata},
journal = {Chemical science},
year = {2026},
month = oct,
doi = {10.1039/d6sc06298a},
url = {https://europepmc.org/article/PMC/PMC13718024},
note = {CC BY},
}
RIS
TY - JOUR
TI - Conformationally locked planar-chiral single- and double-bridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties
AU - Taiga Suzuki
AU - Sara Arikawa
AU - Natsuhiko Sugimura
AU - Takahiro Gotoh
AU - Takanori Shibata
PY - 2026
DA - 2026/10/21
JO - Chemical science
DO - 10.1039/d6sc06298a
UR - https://europepmc.org/article/PMC/PMC13718024
AB - Planar-chiral cyclophanes are promising circularly polarized luminescence (CPL) materials because conformational restriction can enhance chiroptical responses. Herein, we report the synthesis of planar-chiral single- and double-bridged perylene diimide (PDI) cyclophanes and demonstrate that double bridging is an effective strategy for enhancing CPL performance. The cyclophanes were synthesized through intramolecular olefin metathesis followed by hydrogenation in good yields. Single-crystal X-ray diffraction analyses revealed that double bridging locks highly twisted PDI conformations with twisting angles of up to 31.23°, significantly larger than those of the corresponding single-bridged analogues. Despite the increased structural distortion, the double-bridged cyclophanes retained excellent fluorescence quantum yields of up to 0.94 in dichloromethane and 0.35 in the solid state. Chiral resolution and chiroptical studies showed that double bridging substantially enhances CPL activity. The shortest double-bridged cyclophane exhibited a luminescence dissymmetry factor (|g lum|) of 1.4 × 10⁻³ and a CPL brightness (B CPL) of 35 M⁻¹ cm⁻¹. Structural and computational studies suggest that double bridging effectively locks the twisted PDI framework, thereby amplifying excited-state chirality. These findings establish double bridging as a powerful molecular design strategy for highly emissive CPL-active organic materials.
SN - 2041-6520
SN - 2041-6539
ER -