Unravelling the nonlinear optical activity, solvent effects, DFT analysis, and optical waveguide property of pyrrole-derived hydrazone

IF 4.2 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Optical Materials Pub Date : 2025-07-17 DOI:10.1016/j.optmat.2025.117330

Venkatasamy Meenatchi , Sang Jo Lee , Ian John L. Castro , Chong Hoon Kwak , Sung Soo Han

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Abstract

Nonlinear organic hydrazones exhibit exceptional optical waveguide signals, making them promising for fabricating optoelectronic, sensor, and nanophotonic devices. Therefore, this study aims to explore the physicochemical, optical, and nonlinear optical properties of a fluorescent hydrazone N'-((1H-pyrrol-2-yl)methylene)-4-toluenesulfonohydrazide (PTS) synthesized by condensation of 4-toluenesulfonyl hydrazide with pyrrole-2-carboxaldehyde. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and liquid chromatography-mass spectrometry confirmed PTS formation. Powder X-ray diffraction, field emission scanning electron microscopy, and thermogravimetric analysis revealed the phase purity, crystalline structure, and improved thermal stability of PTS. The solvent study results showed significant Stokes-shifted emissions in polar solvents due to the twisted intramolecular charge transfer state. Both solid-state absorption and fluorescence spectra revealed enhanced light-responsiveness and light-emission signals of PTS. A density functional theory analysis was applied to investigate the nonlinear optical property, revealing a high first-order hyperpolarizability (β_tot ≈ 5.938 × 10⁻³⁰ esu) for PTS. Z-scan measurements revealed a nonlinear refractive index change (Δn₀) of 8.5 × 10⁻³, a nonlinear absorption coefficient (β) of 6.9 × 10⁻² cm/W, and a two-photon absorption-related change in absorption (Δα_TPA) of 4.4 × 10³ cm⁻¹. The obtained PTS crystals exhibited green and red dual fluorescence upon optical excitation, as confirmed by confocal fluorescence microscopy studies, indicating its optical wave-guiding potential. The brilliant dual-color fluorescence emission of PTS is crucial for fabricating optoelectronic, optical sensors, and photonic devices.

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揭示非线性光学活性，溶剂效应，DFT分析，以及吡咯衍生腙的光波导特性

非线性有机腙表现出特殊的光波导信号，使它们在光电、传感器和纳米光子器件的制造中具有前景。因此，本研究旨在探讨4-甲苯磺酰肼与吡咯-2-甲醛缩合合成的荧光腙N'-（（1h -吡咯-2-基）亚甲基）-4-甲苯磺酰肼（PTS）的理化、光学和非线性光学性质。傅里叶变换红外光谱、核磁共振光谱和液相色谱-质谱分析证实了PTS的形成。粉末x射线衍射、场发射扫描电镜和热重分析显示了PTS的相纯度、晶体结构和提高的热稳定性。溶剂研究结果表明，极性溶剂中由于分子内电荷转移态的扭曲而产生了明显的斯托克斯位移发射。固体吸收光谱和荧光光谱显示PTS的光响应性和发光信号增强。利用密度泛函理论分析了PTS的非线性光学性质，发现其具有较高的一阶超极化率（βtot≈5.938 × 10−30 esu）。z扫描测量显示非线性折射率变化（Δn0）为8.5 × 10−3，非线性吸收系数（β）为6.9 × 10−2 cm/W，双光子吸收相关的吸收变化（ΔαTPA）为4.4 × 103 cm−1。通过共聚焦荧光显微镜研究证实，所得的PTS晶体在光激发下呈现出绿色和红色双荧光，表明其具有光导波潜力。PTS的明亮双色荧光发射对于制造光电、光学传感器和光子器件至关重要。

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来源期刊

Optical Materials 工程技术-材料科学：综合

CiteScore

6.60

自引率

12.80%

发文量

1265

审稿时长

38 days

期刊介绍： Optical Materials has an open access mirror journal Optical Materials: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. The purpose of Optical Materials is to provide a means of communication and technology transfer between researchers who are interested in materials for potential device applications. The journal publishes original papers and review articles on the design, synthesis, characterisation and applications of optical materials. OPTICAL MATERIALS focuses on: • Optical Properties of Material Systems; • The Materials Aspects of Optical Phenomena; • The Materials Aspects of Devices and Applications. Authors can submit separate research elements describing their data to Data in Brief and methods to Methods X.