化学学报 ›› 2011, Vol. 69 ›› Issue (20): 2499-2504. 上一篇    下一篇

研究论文

三腈基呋喃推拉型电荷转移分子的双光子吸收

吉彦1,钱鹰*,1,周志强2,崔一平2   

  1. (1东南大学化学化工学院 南京 211189)
    (2东南大学先进光子学中心 南京 210096)
  • 投稿日期:2011-01-03 修回日期:2011-04-18 发布日期:2011-06-20
  • 通讯作者: 吉彦 E-mail:jiyan98@163.com
  • 基金资助:

    国家自然科学基金;国家自然科学基金

Two-photon Absorption of a Push-pull Type Intramolecular Charge Transfer Molecule Including Tricyanofuran

Ji Yan1 Qian Ying*,1 Zhou Zhiqiang2 Cui Yiping2   

  1. (1 School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189)
    (2 Advanced Photonics Center, Southeast University, Nanjing 210096)
  • Received:2011-01-03 Revised:2011-04-18 Published:2011-06-20
  • Contact: Yan JI E-mail:jiyan98@163.com

根据双光子吸收效应与分子之间“构效”关系, 设计四种D-π-A推拉偶极型电荷转移分子, 采用AM1方法计算出分子三阶极化率, 筛选出具有潜在三阶非线性光学活性分子2-(3-腈基-(3-(4-(二甲胺基)苯乙烯基)-5,5-二甲环己基-2-烯)甲基)-5,5-二甲基呋喃-2-烯)丙二腈(CFM). 首次在温和条件下使酮羰基与TCF (2-(3-腈基-4,5,5-三甲基呋喃-2-烯)丙二腈)的活泼甲基通过Knoevenagel反应合成出目标分子. 通过非线性透过率法研究了CFM的双光子吸收性质, 采用Ti:Sapphire激光器在800 nm, 150 fs激光激发下测得了CFM的双光子吸收截面σ2, 在DMF溶剂中达到104.29 GM, 在CH2Cl2溶剂中达到78.22 GM. CFM具有较强的双光子吸收特性和光限幅效应.

关键词: 三阶极化率, Knoevenagel反应, 双光子吸收, 推拉型分子

Four D-π-A push-pull type charge transfer molecules were designed basing on the relationship between two-photon absorption and the structure. AM1 method was used to calculate the three-order polarizabilities of the four molecules and the molecule CFM (2-(3-cyano-(3-(4-(dimethyl-amino)styryl)- 5,5-dimethylcyclohex-2-enylidene)methyl)-5,5-dimethylfuran-2-ylidene)malononitrile) was selected out. TCF (2-(3-cyano-4,5,5-trimethylfuran-2-ylidene)malononitrile) used as electronic accepter, N,N-dimethyl- aniline moiety was used as electronic donor, isophorone (3,5,5-trimethylcyclohex-2-enone) as conjugate bridge. CFM was synthesized by Knoevenagel reaction under mild conditions between lively methylene of TCF and ketone. The three-order nonlinear optical property of CFM was got with experiment methods. Using a 800 nm 150 femtosecond Ti:sapphire laser, the CFMs two-photon absorption (2PA) cross-sections reach 104. 29 GM (GM=10-50 cm4•s•photon-1) in DMF and 78.22 GM in CH2Cl2 which obtained by nonlinear transmission method. The CFM has the property of two-photon absorption and optical power limiting.

Key words: three-order polarizability, Knoevenagel reaction, two-photon absorption, push-pull type molecule

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