物理化学学报 >> 2014, Vol. 30 >> Issue (5): 980-986.doi: 10.3866/PKU.WHXB201403031

光化学和辐射化学 上一篇    下一篇

二腈基衍生物的合成及其光限幅性质

汪刘恒1,2, 彭荣宗1,2, 赵榆霞1, 吴飞鹏1   

  1. 1 中国科学院理化技术研究所, 北京100190;
    2 中国科学院大学, 北京100049
  • 收稿日期:2014-01-22 修回日期:2014-02-27 发布日期:2014-04-25
  • 通讯作者: 赵榆霞，吴飞鹏 E-mail:yuxia.zhao@mail.ipc.ac.cn;fpwu@mail.ipc.ac.cn
  • 基金资助:

    国家自然科学基金委员会-中国工程物理研究院NSAF联合基金（U1230123）资助项目

Synthesis and Optical Limiting Behaviors of Malononitrile Derivatives

WANG Liu-Heng1,2, PENG Rong-Zong1,2, ZHAO Yu-Xia1, WU Fei-Peng1   

  1. 1 Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China;
    2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2014-01-22 Revised:2014-02-27 Published:2014-04-25
  • Contact: ZHAO Yu-Xia, WU Fei-Peng E-mail:yuxia.zhao@mail.ipc.ac.cn;fpwu@mail.ipc.ac.cn
  • Supported by:

    The project was supported by the Joint Fund of the National Natural Science Foundation of China and the China Academy of Engineering Physics (U1230123).

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摘要：

设计并合成了一系列含不同末端给电子基团及共轭链长度的1,1-二腈基-2,2-二苯基乙烯类化合物（D1-D7），用核磁共振氢谱（1H NMR）、核磁共振碳谱（13C NMR）和高分辨质谱（HRMS）对分子结构进行了表征.选用N,N-二甲基甲酰胺（DMF）为溶剂，测定了它们的线性光物理性质，用光漂白法研究了它们的光稳定性，用热失重法测试了它们的热稳定性. 研究了这7 个化合物针对800 nm脉冲激光（掺钛蓝宝石激光器，脉冲宽度~130 fs，重复频率1000 Hz）的光限幅性质. 结果表明：以二烷基氨基为给电子基团的4 个化合物（D4-D7）对800 nm的飞秒脉冲激光均具有显著的光限幅性能，限幅机制为双光子吸收（2PA），而端基给电子能力较弱、共轭链长较短的D1-D3光限幅效果并不明显. 此外，D4-D7都具有较好的热稳定性和光稳定性. 而且，该系列化合物的双光子吸收截面、光稳定性和热稳定性都具有随分子结构中给电子基团增强或共轭链增长而增大或提高的趋势. D7具有最好的综合性能，是一个有应用潜力的光限幅材料.

关键词: 光限幅, 800 nm超快激光, 双光子吸收, 非线性透过, 二腈基衍生物

Abstract:

A series of malononitrile derivatives (D1-D7) with different electron donors and conjugation lengths were designed and synthesized. Their structures were characterized using 1H and 13C nuclear magnetic resonance (NMR) spectroscopies, and high-resolution mass spectrometry (HRMS). Their linear photophysical properties were investigated in dimethylformamide (DMF) solutions, their optical stabilities were investigated using photobleaching experiments, and their thermal stabilities were determined using thermogravimetric analysis (TGA). The optical limiting behaviors of D1-D7 under an 800 nm femtosecond pulsed laser (Ti:sapphire laser, ~130 fs, 1000 Hz) were investigated. The results showed that four of the compounds (D4-D7), which had dialkylamines as electron donors, exhibited significant optical limiting behaviors, based on two-photon absorption (2PA), but the other three compounds (D1-D3), which had either weak donors or short conjugation lengths, showed very weak optical limiting behaviors. All the compounds had good photochemical and thermal stabilities. The 2PA cross-sections and optothermal stabilities of this series of compounds increased with increasing conjugation length or electron-donating ability of the alkylamine groups in their structures. D7, which had the best properties, is a potential candidate for optical limiting applications under an 800 nm femtosecond pulsed laser.

Key words: Optical limiting, 800 nm ultrafast laser, Two-photon absorption, Nonlinear transmission, Malononitrile derivative

MSC2000: 

  • O644