化学学报 ›› 2015, Vol. 73 ›› Issue (8): 840-846.DOI: 10.6023/A15040247 上一篇    下一篇

研究论文

1,4-二(4'-N,N-二苯胺基苯乙烯基)苯衍生物单双光子吸收性质的理论研究

王丹a, 郭景富b, 任爱民a, 封继康a, 熊涛c, 肖义c   

  1. a 吉林大学理论化学研究所 长春 130021;
    b 东北师范大学物理学院 长春 130023;
    c 大连理工大学 精细化工国家重点实验室 大连 116012
  • 收稿日期:2015-04-10 出版日期:2015-08-14 发布日期:2015-06-15
  • 通讯作者: 任爱民 E-mail:aimin_ren@yahoo.com
  • 基金资助:

    项目受国家自然科学基金(No. 21173099, 21473071, 20973078)、国家重点研究发展计划(No. 2013CB 834801)及中央高校基本科研项目专项资金资助.

Theoretical Investigations on One and Two-photon Absorption Properties of 1,4-Di(4'-N,N-diphenylaminostyryl)benzene Derivatives

Wang Dana, Guo Jingfub, Ren Aimina, Feng Jikanga, Xiong Taoc, Xiao Yic   

  1. a Institute of Theoretical Chemistry, Jilin University, Changchun 130021;
    b School of Physics, Northeast Normal University, Changchun 130023;
    c State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012
  • Received:2015-04-10 Online:2015-08-14 Published:2015-06-15
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21173099, 21473071 and 20973078), the Major State Basis Research Development Program (No. 2013CB 834801), and the Special Funding to Basic Scientific Research Projects for Central Colleges.

随着双光子显微技术的发展, 获得性质优良的双光子荧光染料成为研究热点. 因此, 通过密度泛函理论(DFT)对一系列D-π-A-π-D型1,4-二(4'-N,N-二苯胺基苯乙烯基)苯(DPA-DSB)衍生物平衡几何结构、电子结构、单双光子吸收以及荧光发射性质进行了理论研究, 对其结构和光学性质的分析表明, 对A, π结构元进行修饰或更换可有效地调节光谱; 向分子片段A引入杂原子可有效提高双光子吸收截面; 和乙烯基团相比, π桥为乙炔基, 若对分子平面性改变不大, 则导致分子双光子吸收截面值减小, 若乙炔桥很大程度改善分子平面性, 则导致分子的TPA截面增大. 本研究旨在理解DPA-DSB衍生物分子结构与双光子性质间的关系, 为设计合成新型双光子材料提供重要信息.

关键词: DPA-DSB衍生物, 单光子吸收, 荧光发射, 双光子吸收, 双光子吸收截面

With the development of two-photon microscopy, getting excellent two-photon fluorescence dyes become a hot topic. In this work, the equilibrium geometries, electronic structures, one- and two-photon absorption properties and the fluorescent emission properties for a series of D-π-A-π-D type 1,4-di(4'-N,N-diphenylaminostyryl)benzene (DPA-DSB) derivatives were investigated by the density functional theory (DFT). The results show that the one photon absorption wavelengths of this series of one-dimensional linear conjugated molecules are in the range 370~540 nm, fluorescence emission wavelengths are in the range 435~700 nm, provided the absorption of the UV to green light and the emission of the all visible range. The Stokes shifts are in the 47~270 nm range. Thus, these molecules provide broad color fluorophore options molecules for biological fluorescence imaging and fluorescence microscopy. The response function approach has been used to calculate the two-photon properties. Analysis of two-photon properties of these molecules suggests that these molecules two-photon absorption wavelengths are at 650~880 nm. The molecules 2, 4, 5, 6, 8 and 12, 14 have two-photon absorption in the infrared light range, which means these molecules can be used as alternative molecules to design the infrared medical material. These molecules have the fluorescence signal in the visible range and excellent two-photon characteristics; can be used as two-photon fluorescent probes biomarkers and alternative materials. Analyzing its structure and optical properties indicate that the modification or replacement of the electron-withdrawing group in the center of the molecule can effectively shift its electronic spectrum, the addition of N atom or S atom can significantly improve the two-photon absorption cross-section. For the acetylenyl moiety as π bridge, if the molecular plane did not change compared with ethylene bridge, it makes the two-photon absorption cross-section decreases; if acetylene bridge improved the planarity of molecule, it causes two-photon absorption cross-section increases. This study aims to understand the relationship between molecular structure and two-photon properties and offer some important information for the design and synthesis of novel materials.

Key words: DPA-DSB derivative, one-photon absorption, fluorescence emission, two-photon absorption, two-photon absorption cross-section