Scholarlink

<p>High-performance organic second-order nonlinear optical (NLO) crystals face a persistent challenge. Molecular designs that enhance hyperpolarizability often crystallize into centrosymmetric or nonpolar arrangements, suppressing bulk second-order response. Simultaneously, strategies that increase hyperpolarizability typically reduce optical bandgaps, enforcing a trade-off between nonlinearity and transparency. We report a chirality-driven lattice engineering strategy that couples molecular asymmetry with directional intermolecular interactions to promote polar ordering. A binaphthyl-based chromophore (S-3) crystallizes in the polar space group <i>P</i>2<sub>1</sub> exhibiting strong second-harmonic generation (∼3.53 × KDP), wide transparency (3.91 eV), phasematchable birefringence (Δ<i>n</i> = 0.15), high laser damage threshold (742.6 MW cm<sup>−2</sup>), and thermal stability (210 °C). Theoretical calculation reveals a 69% enhancement in first-order hyperpolarizability (<i>β</i><sub>tot</sub>) relative to the unfunctionalized derivative, with a net intramolecular electron transfer of 0.16 e<sup>−</sup> from the chiral scaffold to the benzoate acceptor. Crucially, enantiomeric crystals exhibit identical NLO responses, confirming that the bulk nonlinearity is governed by the engineered lattice polarity, not molecular handedness. This work establishes chirality as a powerful active tool for crystal engineering and provides a general design paradigm for high-performance organic NLO materials.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Chirality-driven polar lattice engineering for high-performance organic nonlinear optical crystals

  • 期刊论文

  • 发表日期：

    2026年4月7日

查看全文
  • Bo Liu,
  • Jia-Li Chen,
  • Yu-Peng Han,
  • Qiao-Hong Li,
  • Shangda Li,
  • Fei Wang,
  • Jian Zhang

摘要

High-performance organic second-order nonlinear optical (NLO) crystals face a persistent challenge. Molecular designs that enhance hyperpolarizability often crystallize into centrosymmetric or nonpolar arrangements, suppressing bulk second-order response. Simultaneously, strategies that increase hyperpolarizability typically reduce optical bandgaps, enforcing a trade-off between nonlinearity and transparency. We report a chirality-driven lattice engineering strategy that couples molecular asymmetry with directional intermolecular interactions to promote polar ordering. A binaphthyl-based chromophore (S-3) crystallizes in the polar space group P21 exhibiting strong second-harmonic generation (∼3.53 × KDP), wide transparency (3.91 eV), phasematchable birefringence (Δn = 0.15), high laser damage threshold (742.6 MW cm−2), and thermal stability (210 °C). Theoretical calculation reveals a 69% enhancement in first-order hyperpolarizability (βtot) relative to the unfunctionalized derivative, with a net intramolecular electron transfer of 0.16 e− from the chiral scaffold to the benzoate acceptor. Crucially, enantiomeric crystals exhibit identical NLO responses, confirming that the bulk nonlinearity is governed by the engineered lattice polarity, not molecular handedness. This work establishes chirality as a powerful active tool for crystal engineering and provides a general design paradigm for high-performance organic NLO materials.