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<p>To explore the unique optoelectronic potential of alkalides, a series of nine alkalide complexes based on the aza-12-crown-4 are designed by placing alkali metal atoms both inside and outside the complexant, forming complexes of the type M⁺(aza-12-crown-4)Mˉ, where Mˉ = Li, Na, or K. The electronic properties are investigated through natural bond orbital (NBO) and frontier molecular orbital (FMO) analyses. These analyses collectively confirm the alkalide nature of the designed complexes by revealing negative charge and position of highest occupied molecular orbital (HOMO) over external alkali metals. Furthermore, partial density of state (PDOS) spectra are generated to validate the alkalide nature of complexes. The complexes exhibit relatively low HOMO-LUMO energy gaps (2.85–4.01&#xa0;eV) compared to aza-12-crown-4 (9.93&#xa0;eV), leading to increased electronic conductivity. The designed alkalides display remarkable nonlinear optical responses with high first hyperpolarizability ranging from 7.18 × 10<sup>3</sup> to 2.00 × 10<sup>5</sup> a.u. credited to low their vertical ionization potential (2.77–3.79&#xa0;eV) and excitation energies (0.95 to 2.13&#xa0;eV) values. The vector component of hyperpolarizability (β<sub>vec</sub>) is calculated to assess the alignment of hyperpolarizability along the dipole moment direction. Furthermore, a two-level model analysis is performed to find hyperpolarizability values at excited states. The complexes show absorption maxima in the visible and infrared regions (580–1301&#xa0;nm) which gives their applicability from visible photonics to IR communication technologies. We hope this work could open up a new strategy to design efficient NLO materials using aza-12-crown-4 complexant and encourage the experimental efforts in the laboratory to synthesize such stable complexes.</p> Graphical Abstract <p></p>

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Charge-localized aza-12-crown based alkalides with exceptional nonlinear optical response

  • 期刊论文

  • 发表日期：

    2026年1月12日

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  • Jabir Hussain,
  • Rana Farhat Mehmood,
  • Riaz Hussain,
  • Sarah Tariq,
  • Mashal Farooq,
  • Muhammad Arshad,
  • Ajaz Hussain,
  • Khurshid Ayub

摘要

To explore the unique optoelectronic potential of alkalides, a series of nine alkalide complexes based on the aza-12-crown-4 are designed by placing alkali metal atoms both inside and outside the complexant, forming complexes of the type M⁺(aza-12-crown-4)Mˉ, where Mˉ = Li, Na, or K. The electronic properties are investigated through natural bond orbital (NBO) and frontier molecular orbital (FMO) analyses. These analyses collectively confirm the alkalide nature of the designed complexes by revealing negative charge and position of highest occupied molecular orbital (HOMO) over external alkali metals. Furthermore, partial density of state (PDOS) spectra are generated to validate the alkalide nature of complexes. The complexes exhibit relatively low HOMO-LUMO energy gaps (2.85–4.01 eV) compared to aza-12-crown-4 (9.93 eV), leading to increased electronic conductivity. The designed alkalides display remarkable nonlinear optical responses with high first hyperpolarizability ranging from 7.18 × 103 to 2.00 × 105 a.u. credited to low their vertical ionization potential (2.77–3.79 eV) and excitation energies (0.95 to 2.13 eV) values. The vector component of hyperpolarizability (βvec) is calculated to assess the alignment of hyperpolarizability along the dipole moment direction. Furthermore, a two-level model analysis is performed to find hyperpolarizability values at excited states. The complexes show absorption maxima in the visible and infrared regions (580–1301 nm) which gives their applicability from visible photonics to IR communication technologies. We hope this work could open up a new strategy to design efficient NLO materials using aza-12-crown-4 complexant and encourage the experimental efforts in the laboratory to synthesize such stable complexes.

Graphical Abstract