具有强双光子吸收和高双光子荧光活性的全芳香DPP基共轭分子及其构建单/双光子荧光化学传感器研究

项目名称： 具有强双光子吸收和高双光子荧光活性的全芳香DPP基共轭分子及其构建单/双光子荧光化学传感器研究

项目编号： No.51473084

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 一般工业技术

项目作者： 杨文君

作者单位： 青岛科技大学

项目金额： 83万元

中文摘要： 尽管人们已经设计合成了大量双光子活性的共轭有机分子，但具有大双光子吸收截面（δ）的几乎都是以碳-碳双键或叁键为共轭桥，存在光、热及化学稳定性等问题，而且鲜见高δ共轭有机分子用作离子和/或分子双光子荧光化学传感器的成功报道。本项目通过3,6-二芳基吡咯并吡咯二酮（DPP）与某些芳基化合物的交叉Suzuki偶合,设计合成一系列包括带有功能活性单元的高光热稳定性全芳香DPP基共轭小分子和高分子，首次测定研究它们的强双光子吸收性质和高双光子激发荧光活性，首次构筑能够对某些阴/阳离子进行双光子荧光化学传感的全芳香大δ共轭有机荧光分子，建立全芳香DPP基双光子荧光共轭分子的化学组成、结构与性能及功能关系。本项目不仅拓展了DPP基共轭分子的种类和应用范围，而且为双光子科学和技术发展提供了新的高性能和多功能共轭有机高双光子活性材料体系，具有重要的理论意义和实际意义。

中文关键词： 全芳香共轭分子；双光子吸收；双光子荧光；双光子荧光化学传感器；吡咯并吡咯二酮

英文摘要： Two-photon absorption (2PA) and two-photon excitation fluorescence (2PEF) have many advantages over commonly UV-vis one-photon ones, including exclusive confinement of the excitation to the focal volume with high 3D resolution and reduced photobleaching and phototoxicity by virtue of the low-energy NIR excitation with greater depths of penetration. Organic conjugated molecules (small and polymeric compounds) with large 2PA cross sections have attracted considerable interests because of their significant applications in the areas of nonlinear optical materials, such as two-photon excited fluorescence microscopy, optical limiting, optical data storage, 3D-microfabrication, up-conversion lasing, photodynamic cancer therapy, and two-photon fluorescent probes. It is very desirable that 2PA materials not only have large 2PA cross sections but also exhibite good photo- and thermal-stability and so on, moreover, the functional units that can act with analytes to induce the significant changes of emission intensity or fluorescence color are also hoped earnestly if TPA materials are used as two-photon fluorescent probes such as for anion/metal ions. It is well known that conjugated polymers can offer a significant advantage over small chromophores for sensor applications, that is singal amplification effect and higher sensitivity due to their conjugated backbone allowing efficient electron delocalization and exciton migration over long distance. However,to the best of our knowledge, there have been a few fully aromatic conjugated polymers with very large 2PA cross-sections as well as conjugated polymer-based two-photon ion sensors reported in the literature.In this project, a series of fully aromatic 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole (DPP)- containing copolymers were designed and synthesized by Suzuki cross-coupling between mono-/bis-substituted DPP and various aromatic or heteroaromatic monomers, and their one- and two-photon absorption and emission properties, sensing performance for fluoride, zinc and hydroxide ions, optical power limiting were investigated in order to develop novel high-performance and multifunctional two-photon active dyes. To the best of our knowlege, many attempts have been made to use DPP-based copolymers as highly luminescent, electroactive and photoactive materials, but there are few reports on the 2PA properties and applications of DPP-based conjugated molecules. These polymers studied here posess D-π-A-π-D-type repeating units, and some of them have specific functional units selectively for fluoride ion or zinc ion or Pt ion, etc. to endow them with very large 2PA cross-sections and strong two-photon excited fluorescence and exhibit promising optical limiting and sensing-ion properties which based on intramolecular charge transfer effect or complexation. Pre-experiments have been carried out and advanced the feasibility of the design ideas and the realization of the research objects.

英文关键词： fully aromatic conjugated molecules;strong two-photon absorption;high two-photon excitation fluorescence activity;two-photon chemosensor;diketopyrrolopyrrole