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<p>Chiroptical materials combining chirality with second-harmonic generation are attractive for polarization-resolved photonics, yet examples integrating strong chiroptical nonlinear activity, broad infrared transparency and inorganic robustness remain limited. Here we report a purely inorganic strategy in which molecular-level geometric distortion of intrinsically <i>C</i><sub>1</sub>-symmetric phosphorus–chalcogen cages tunes second-harmonic generation circular dichroism (SHG-CD). Site-selective homologous substitution yields enantiopure molecular cage crystals, <i>S</i>/<i>R</i>-P<sub>4</sub>S<sub>5</sub>, <i>S</i>/<i>R</i>-AsP<sub>3</sub>S<sub>5</sub>, <i>S</i>/<i>R</i>-P<sub>4</sub>S<sub>4</sub>Se and <i>S</i>/<i>R</i>-AsP<sub>3</sub>S<sub>4</sub>Se, spanning a controlled distortion series. These crystals exhibit pronounced SHG-CD, with <InlineEquation ID="IEq1"><EquationSource Format="TEX">\({{\mbox{g}}}_{{\mbox{SHG}}-{\mbox{CD}}}\)</EquationSource><EquationSource Format="MATHML"><math><msub><mrow><mstyle><mtext>g</mtext></mstyle></mrow><mrow><mstyle><mtext>SHG</mtext></mstyle><mo>−</mo><mstyle><mtext>CD</mtext></mstyle></mrow></msub></math></EquationSource></InlineEquation> = 0.48–1.70 under 1064 nm excitation, strong SHG outputs of 1.1–2.8 × AgGaS<sub>2</sub> at 2050 nm, broad infrared transparency and high laser-induced damage thresholds. Across this series, SHG-CD correlates with distortion-driven molecular asymmetry, indicating that the cage dipole moment can serve as a practical descriptor for chiroptical nonlinear response within this isostructural molecular cage family. These results establish inorganic molecular cages as a tunable chiroptical nonlinear platform for infrared-transparent chiroptical nonlinear materials.</p>

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Distortion-engineered C1-symmetric inorganic molecular cages enable tunable chiroptical nonlinear optics with broad infrared transparency

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  • 发表日期：

    2026年8月1日

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  • Chao Wang,
  • Chensheng Lin,
  • Xiaoying Shang,
  • Xingwang Zhu,
  • Shunda Yang,
  • Tao Yan,
  • Chengming Hu,
  • Min Luo

摘要

Chiroptical materials combining chirality with second-harmonic generation are attractive for polarization-resolved photonics, yet examples integrating strong chiroptical nonlinear activity, broad infrared transparency and inorganic robustness remain limited. Here we report a purely inorganic strategy in which molecular-level geometric distortion of intrinsically C1-symmetric phosphorus–chalcogen cages tunes second-harmonic generation circular dichroism (SHG-CD). Site-selective homologous substitution yields enantiopure molecular cage crystals, S/R-P4S5, S/R-AsP3S5, S/R-P4S4Se and S/R-AsP3S4Se, spanning a controlled distortion series. These crystals exhibit pronounced SHG-CD, with \({{\mbox{g}}}_{{\mbox{SHG}}-{\mbox{CD}}}\)gSHG−CD = 0.48–1.70 under 1064 nm excitation, strong SHG outputs of 1.1–2.8 × AgGaS2 at 2050 nm, broad infrared transparency and high laser-induced damage thresholds. Across this series, SHG-CD correlates with distortion-driven molecular asymmetry, indicating that the cage dipole moment can serve as a practical descriptor for chiroptical nonlinear response within this isostructural molecular cage family. These results establish inorganic molecular cages as a tunable chiroptical nonlinear platform for infrared-transparent chiroptical nonlinear materials.