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<p>Single crystals of the organic–inorganic hybrid bis((pyridin-1-ium-3-yl)methanaminium) hexachlorostannate(IV) dichloride, ([3-PyCH<sub>2</sub>NH<sub>3</sub>]<sub>2</sub>[SnCl<sub>6</sub>]Cl<sub>2</sub>), were grown and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes as a centrosymmetric structure comprising discrete octahedral [SnCl<sub>6</sub>]<sup>2–</sup> anions linked to protonated organic cations through charge-assisted N–H···Cl hydrogen bonds, forming a stable supramolecular framework. Bond valence sum calculations confirm the + 4 oxidation state of tin, supporting the structural model. Diffuse reflectance spectroscopy reveals a wide optical bandgap of 4.28&#xa0;eV, indicating insulating behavior typical of chloride-based hybrids. Photoluminescence measurements show near-ultraviolet emission at room temperature, attributed to ligand-centered electronic transitions within the organic component. Third-order non-linear optical measurements demonstrate a measurable χ<sup>(3)</sup> value on the order of 10<sup>–11</sup> esu, suggesting significant electronic polarization despite the centrosymmetric lattice. Dielectric analysis indicates strong frequency and temperature-dependent behavior, with higher dielectric constants at low frequencies due to interfacial and space-charge polarization, followed by stabilization at higher frequencies. AC conductivity studies suggest a transition from polarization-dominated transport to thermally activated hopping conduction. Hirshfeld surface analysis confirms that N–H···Cl hydrogen bonding dominates crystal packing. These results demonstrate the key role of hydrogen-bond-driven organization in determining the optical and dielectric properties of this hybrid material.</p>

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An organic–inorganic hexachlorostannate(IV) hybrid: structure, dielectric properties, and third-order nonlinear optical response

  • 期刊论文

  • 发表日期：

    2026年5月8日

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  • Pirnazar Kodamboevich Kodamboev,
  • Hela Ferjani,
  • Khayitali Fayzullaevich Adinaev,
  • Rajamanickam Duraisamy,
  • Elyorbek Shonazar ugli Samandarov,
  • Sadridin Eshkaraev,
  • Surayyo Razzoqovna Razzoqova,
  • Sabokhat Babaevna Sadikova,
  • Aziz Bakhtiyarovich Ibragimov,
  • Tarek A. Yousef,
  • Yasmeen G. Abou El-Reash,
  • Balakrishnan Chellakarungu

摘要

Single crystals of the organic–inorganic hybrid bis((pyridin-1-ium-3-yl)methanaminium) hexachlorostannate(IV) dichloride, ([3-PyCH2NH3]2[SnCl6]Cl2), were grown and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes as a centrosymmetric structure comprising discrete octahedral [SnCl6]2– anions linked to protonated organic cations through charge-assisted N–H···Cl hydrogen bonds, forming a stable supramolecular framework. Bond valence sum calculations confirm the + 4 oxidation state of tin, supporting the structural model. Diffuse reflectance spectroscopy reveals a wide optical bandgap of 4.28 eV, indicating insulating behavior typical of chloride-based hybrids. Photoluminescence measurements show near-ultraviolet emission at room temperature, attributed to ligand-centered electronic transitions within the organic component. Third-order non-linear optical measurements demonstrate a measurable χ(3) value on the order of 10–11 esu, suggesting significant electronic polarization despite the centrosymmetric lattice. Dielectric analysis indicates strong frequency and temperature-dependent behavior, with higher dielectric constants at low frequencies due to interfacial and space-charge polarization, followed by stabilization at higher frequencies. AC conductivity studies suggest a transition from polarization-dominated transport to thermally activated hopping conduction. Hirshfeld surface analysis confirms that N–H···Cl hydrogen bonding dominates crystal packing. These results demonstrate the key role of hydrogen-bond-driven organization in determining the optical and dielectric properties of this hybrid material.