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<p>Superhalogens, owing to their higher electron affinities than conventional halogens, possess exceptional electron-accepting capabilities, making them attractive candidates for tuning nonlinear optical (NLO) properties. In this study, we systematically investigated the NLO behavior of superhalogen-doped hexaazakekulene (M1) macrocycles using density functional theory (DFT) through both static and dynamic hyperpolarizability analyses. The electronic and thermodynamic stabilities of the doped systems are evaluated via interaction energies (E<sub>int</sub>), vertical ionization energies (<i>I</i>), and frontier molecular orbital (FMO) analysis. Among the studied complexes, CaF<sub>3</sub>–M1 exhibits the highest interaction energy (− 68.33&#xa0;kcal mol⁻¹), indicating superior binding stability. Static and dynamic NLO analyses revealed substantial improvements in optical responses upon doping. Among the designed systems, MgF<sub>3</sub>-M1 exhibited the highest static first hyperpolarizability (8.77 × 10<sup>4</sup> au) and lowest excitation energy (0.90&#xa0;eV), aligning with the two-level model predictions. Frequency-dependent studies at 532&#xa0;nm and 1064&#xa0;nm confirmed enhanced electro-optic Pockels effects and second harmonic generation (SHG), with BeF<sub>3</sub>-M1 and CaF<sub>3</sub>-M1 showing particularly strong responses. These variations are attributed to the atomic size and electronic characteristics of the dopant metals. Third-order NLO behavior was also analyzed, showing significant enhancements in second hyperpolarizability (γ) and nonlinear refractive index (n<sub>2</sub>), especially for CaF<sub>3</sub>-M1. UV–Vis spectral analysis revealed bathochromic shifts and dual absorption bands, confirming extended π-conjugation and distinct electronic transitions. Overall, superhalogen doping of M1 macrocycles results in remarkable improvements in NLO activity, stability, and optical tunability. These findings highlight their strong potential as advanced materials for photonic and optoelectronic applications.</p>

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Correlation between structural features and optoelectronic properties in superhalogen doped hexaazakekulenes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月29日

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  • Naveen Kosar,
  • Tariq Mahmood,
  • Sumayya M. Ansari,
  • Mazhar Amjad Gilani,
  • Muhammad Ajmal,
  • Mohammed Salim Akhter,
  • Muhammad Imran,
  • Adnan Younis

摘要

Superhalogens, owing to their higher electron affinities than conventional halogens, possess exceptional electron-accepting capabilities, making them attractive candidates for tuning nonlinear optical (NLO) properties. In this study, we systematically investigated the NLO behavior of superhalogen-doped hexaazakekulene (M1) macrocycles using density functional theory (DFT) through both static and dynamic hyperpolarizability analyses. The electronic and thermodynamic stabilities of the doped systems are evaluated via interaction energies (Eint), vertical ionization energies (I), and frontier molecular orbital (FMO) analysis. Among the studied complexes, CaF3–M1 exhibits the highest interaction energy (− 68.33 kcal mol⁻¹), indicating superior binding stability. Static and dynamic NLO analyses revealed substantial improvements in optical responses upon doping. Among the designed systems, MgF3-M1 exhibited the highest static first hyperpolarizability (8.77 × 104 au) and lowest excitation energy (0.90 eV), aligning with the two-level model predictions. Frequency-dependent studies at 532 nm and 1064 nm confirmed enhanced electro-optic Pockels effects and second harmonic generation (SHG), with BeF3-M1 and CaF3-M1 showing particularly strong responses. These variations are attributed to the atomic size and electronic characteristics of the dopant metals. Third-order NLO behavior was also analyzed, showing significant enhancements in second hyperpolarizability (γ) and nonlinear refractive index (n2), especially for CaF3-M1. UV–Vis spectral analysis revealed bathochromic shifts and dual absorption bands, confirming extended π-conjugation and distinct electronic transitions. Overall, superhalogen doping of M1 macrocycles results in remarkable improvements in NLO activity, stability, and optical tunability. These findings highlight their strong potential as advanced materials for photonic and optoelectronic applications.