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<p>The precise control of stereochemistry in organic <i>π</i>-conjugated chiral foldamers remains a fundamental challenge in synthetic chemistry due to the lack of universal design principles. Herein, we establish a versatile strategy through cascade integration using a chiral building block <b>I-1</b> as a stereochemical template. Sequential imide functionalization yields <b>I-2</b>, followed by parallel <i>π</i>-layer installation and structural expansion to construct foldamers <b>II-1</b>, <b>II-2</b>, <b>III-1</b>, and <b>III-2</b>, featuring naphthalimide bridges that interconnect distinct layers with preserved chirality. X-ray crystallography and electrostatic potential analysis conclusively resolve the layered architecture, multi-chiral elements and absolute configurations of this novel folding system. Frontier molecular orbitals and photophysical studies reveal unique luminescent properties arising from the naphthalimide core. The performance characterization indicates that both PLQY and the dissymmetry factors (<i>g</i><sub>abs</sub>/<i>g</i><sub>lum</sub>) of chiroptical properties exhibit significant dependence on spatial modulation. Racemization kinetics and theoretical simulation show that <i>π</i>-layer incorporation significantly enhances interlayer van der Waals interactions, elevating the racemization Gibbs free energy to 41 kcal/mol for <b>II-1</b>, which improvement over reported analogues. This work establishes a rational design platform for <i>π</i>-conjugated chiral foldamers, enabling the construction of configurationally stable, geometrically precise architectures with tailored optical properties.</p>

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Naphthalimide-based π-conjugated chiral foldamers: cascade-integrated construction strategy, structural analysis and chiroptical properties

  • 期刊论文

  • 发表日期：

    2025年8月7日

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  • Hao Hu,
  • Qinlin Yuan,
  • Jialin Xie,
  • Hongtao Liu,
  • Weijie Chi,
  • Jianwei Li,
  • Chunman Jia

摘要

The precise control of stereochemistry in organic π-conjugated chiral foldamers remains a fundamental challenge in synthetic chemistry due to the lack of universal design principles. Herein, we establish a versatile strategy through cascade integration using a chiral building block I-1 as a stereochemical template. Sequential imide functionalization yields I-2, followed by parallel π-layer installation and structural expansion to construct foldamers II-1, II-2, III-1, and III-2, featuring naphthalimide bridges that interconnect distinct layers with preserved chirality. X-ray crystallography and electrostatic potential analysis conclusively resolve the layered architecture, multi-chiral elements and absolute configurations of this novel folding system. Frontier molecular orbitals and photophysical studies reveal unique luminescent properties arising from the naphthalimide core. The performance characterization indicates that both PLQY and the dissymmetry factors (gabs/glum) of chiroptical properties exhibit significant dependence on spatial modulation. Racemization kinetics and theoretical simulation show that π-layer incorporation significantly enhances interlayer van der Waals interactions, elevating the racemization Gibbs free energy to 41 kcal/mol for II-1, which improvement over reported analogues. This work establishes a rational design platform for π-conjugated chiral foldamers, enabling the construction of configurationally stable, geometrically precise architectures with tailored optical properties.