Structure-property relationships in morpholinium hexahalostannate(IV) hybrid materials: Impact of halide substitution on optical and nonlinear responses

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-09-13 DOI:10.1016/j.jssc.2025.125665

Pirnazar Kodamboevich Kodamboev , Hela Ferjani , Yasmeen G. Abou El-Reash , Tarek A. Yousef , Ikrom Iskandarovich Abdullaev , Loganathan Guganathan , Takhirov Yuldash Rajabovich , Elyorbek Shonazar ugli Samandarov , Aziz Bakhtiyarovich Ibragimov , Chellakarungu Balakrishnan

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Abstract

Two novel morpholinium-based organic-inorganic hybrid halostannates, (MorphH₂)SnCl₆.2Cl, (1), and (MorphH₂)SnBr₆.2H₂O (2), {(Morph)= (4-(2-ammonioethyl)morpholin-4-ium)} were synthesized using slow evaporation at room temperature technique and carefully characterized. Single-crystal X-ray diffraction validated nearly perfect octahedral geometries surrounding the Sn(IV) centers in both compounds. The Hirshfeld surface and 2D-fingerprintplot analysis indicated predominant halogen and hydrogen bonding, which enhances supramolecular stability. Optical tests revealed a notable halide-dependent redshift in the direct band gap, diminishing from 4.36 eV (Cl⁻) to 2.99 eV (Br⁻), with photoluminescence investigations supporting this observation. Z-scan measurements revealed significant third-order nonlinear optical (NLO) responses, with χ⁽³⁾ values of 9.22 × 10⁻¹² esu for sample (1) and an exceptional 5.00 × 10⁻¹¹ esu for sample (2). Moreover, frequency and temperature-dependent dielectric analysis elucidated space charge and dipolar relaxation mechanisms. These findings highlight the efficacy of halide substitution, hydration state and crystal symmetry in modulating the structural and functional characteristics of tin-based hybrids, establishing them as viable candidates for photonic, nonlinear optical, and dielectric device applications.

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六卤丁酸morpholinium （IV）杂化材料的结构性质关系：卤化物取代对光学和非线性响应的影响

采用室温慢蒸发技术合成了两种新型的基于MorphH2的有机-无机杂化盐（MorphH2）SnCl6.2Cl,(1)和（MorphH2）SnBr6.2H2O (2) {(Morph)=(4-（2-氨乙基）morpholin-4-ium)}，并对其进行了表征。单晶x射线衍射证实了两种化合物中Sn（IV）中心周围的近乎完美的八面体几何形状。Hirshfeld表面和2d指纹图谱分析表明，卤素和氢键为主，增强了超分子稳定性。光学测试显示，在直接带隙中有明显的卤化物相关红移，从4.36 eV （Cl−）减小到2.99 eV (Br−)，光致发光研究支持了这一观察结果。z -扫描测量显示了显著的三阶非线性光学（NLO）响应，样品(1)的χ(3)值为9.22 × 10−12 esu，样品(2)的χ(3)值为5.00 × 10−11 esu。此外，频率和温度相关的介电分析阐明了空间电荷和偶极弛豫机制。这些发现强调了卤化物取代、水化状态和晶体对称在调节锡基杂化材料结构和功能特性方面的有效性，使其成为光子、非线性光学和介电器件应用的可行候选材料。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.