基于吩噻嗪的 α， β 不饱和酮衍生物的合成及其非线性光学特性

doi:10.11901/1005.3093.2025.182

材料研究学报

2026, Vol. 40

Issue (4): 305-312 DOI: 10.11901/1005.3093.2025.182

研究论文

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基于吩噻嗪的 α， β 不饱和酮衍生物的合成及其非线性光学特性

陈松华¹^,², 朱祥钊³, 胡红丹³, 薛凯³, 宋瑛林⁴, 辛丹丹¹, 卢亚琦², 林水东², 袁耀锋³(

)

^1.通辽职业学院药品食品系通辽 028000
^2.龙岩学院化学与材料学院龙岩 364012
^3.福州大学化学学院福州 350108
^4.苏州大学物理科学与技术学院苏州 215006

Synthesis and Nonlinear Optical Properties of Phenothiazine-functionalized α, β-unsaturated Ketone Derivatives

CHEN Songhua¹^,², ZHU Xiangzhao³, HU Hongdan³, XUE Kai³, SONG Yinglin⁴, XIN Dandan¹, LU Yaqi², LIN Shuidong², YUAN Yaofeng³(

)

^1.Department of Pharmacy and Food, Tongliao Vocational College, Tongliao 028000, China
^2.College of Chemistry and Material, Longyan University, Longyan 364012, China
^3.College of Chemistry, Fuzhou University, Fuzhou 350108, China
^4.School of Physical Science and Technology, Soochow University, Suzhou 215006, China

引用本文:

陈松华, 朱祥钊, 胡红丹, 薛凯, 宋瑛林, 辛丹丹, 卢亚琦, 林水东, 袁耀锋. 基于吩噻嗪的 α， β 不饱和酮衍生物的合成及其非线性光学特性[J]. 材料研究学报, 2026, 40(4): 305-312.
Songhua CHEN, Xiangzhao ZHU, Hongdan HU, Kai XUE, Yinglin SONG, Dandan XIN, Yaqi LU, Shuidong LIN, Yaofeng YUAN. Synthesis and Nonlinear Optical Properties of Phenothiazine-functionalized α, β-unsaturated Ketone Derivatives[J]. Chinese Journal of Materials Research, 2026, 40(4): 305-312.

全文: PDF(3622 KB) HTML

摘要:

以吩噻嗪为电子给体单元，设计并合成两种具有α, β-不饱和酮构型的对称型有机分子(1E,4E)-1,5-双(4-(10H-吩噻嗪-10-基)苯基)戊-1,4-二烯-3-酮(COP)和2-((1E,4E)-1,5-双(4-(10H-吩噻嗪-10-基)苯基)戊-1,4-二烯-3-亚基)丙二腈(CNP)，研究了这类化合物的物理和三阶非线性光学性能。结果表明：在532 nm的激光作用下，COP和CNP呈现出反饱和的双光子吸收特性(吸收系数分别为COP: 1.2 × 10^-11 m/W和CNP: 4.0 × 10^-11 m/W)，其中CNP的非线性响应比COP强。在CNP分子中引入电子受体二氰基亚乙基基团，使其最大吸收峰比COP红移了69 nm。同时，根据瞬态吸收光谱确定了CNP分子的非线性吸收主要来源于激发态的电荷转移过程。进一步进行理论计算，分析了CNP分子激发态的电荷和空穴分布。结果表明，引入吸收电子能力更强的受体基团，使CNP分子的前沿分子轨道能隙更小、电荷转移距离更长和电子离域能力更强。

关键词 ：有机高分子材料, 三阶非线性光学, Z扫描, 分子内电荷转移化合物, 吩噻嗪

Abstract：

In this study, two symmetric organic molecules with α,β-unsaturated ketone configuration, i.e., COP and CNP, were designed and synthesized with phenothiazine as an electron donor, and their photophysical and third-order nonlinear optical properties were investigated. Due to the introduction of the electron-withdrawing dicyanoethene group in the CNP molecule, its maximum absorption peak red-shifted by approximately 60 nm, in comparison to that of the COP. Furthermore, under the irradiation of a 532 nm laser, both CNP and COP exhibited reverse-saturable two-photon absorption characteristics. However, CNP showed a significantly higher absorption coefficient (COP: 1.2 × 10^-11 m/W and CNP: 4.0 × 10^-11 m/W), indicating a stronger nonlinear optical response. To determine the origin of this performance discrepancy, the nonlinear absorption of CNP molecules was first identified to primarily arise from the charge transfer process in the excited state through transient absorption spectroscopy. Subsequently, theoretical calculations were employed to analyze the charge and hole distribution of CNP molecules in the excited state. The results revealed that the introduction of a stronger electron-withdrawing receptor group led to a smaller energy gap in the frontier molecular orbitals, a longer charge transfer distance, and enhanced electron delocalization ability in CNP molecules. These findings provide a meaningful reference for designing organic molecular materials with superior nonlinear optical properties.

Key words： organic polymer materials third-order nonlinear optics Z-scanning intramolecular charge transfer compounds phenothiazine

收稿日期: 2025-05-29

ZTFLH:

O430.50

基金资助:国家自然科学基金(22071025);国家自然科学基金(22373019);福厦泉国家自主创新示范区金属基功能材料协同创新平台项目(2022-P-021);福建省自然科学基金(2025J01384);福建省自然科学基金(2023J01982);福建省教育厅中青年人才科研项目(JAT231118)

通讯作者: 袁耀锋，教授，yaofeng_yuan@fzu.edu.cn，研究方向为有机合成及金属有机化学;

Corresponding author: YUAN Yaofeng, Tel: 13655089601, E-mail: yaofeng_yuan@fzu.edu.cn

作者简介: 陈松华，男，1985年生，副教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2025.182 或 https://www.cjmr.org/CN/Y2026/V40/I4/305

图1 化合物 COP和CNP的合成路线

图2 COP和CNP的紫外吸收和荧光发射光谱

图3 532 nm 波长下的开孔 Z 扫描实验数据

图4 COP和CNP的飞秒瞬态吸收光谱和瞬态吸收光谱随时间变化的演化曲线

图5 COP和CNP的HOMOs和LUMOs的电子密度分布

图6 COP和CNP的前沿分子轨道的电子云分布

表1 COP和CNP中的电子和空穴数据

图7 COP和CNP的电子和空穴分布以及正负电荷中心

图8 COP和CNP的TDM热图

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