具有高双光子吸收截面的卟啉、酞菁类纳米材料的可控制备及性能研究

Recently, organic two-photon absorption materials have attracted considerable attention due to their potential applications including three-dimensional optical memory, optical power limiting, two-photon photodynamic therapy and fluorescence microscopy. There is still a challenge in the design and synthesis of organic materials with large two-photon absorption cross section. Phthalocyanines and porphyrins are suitable candidates as two-photon absorption materials not only because of their large π-electron system with two-dimensional conjugated electronic molecular structure but also because of their exceptional chemical and thermal stability, versatile functionalization at the peripheral positions and various possibilities of the central metal ion. In this project, we will try to explore efficient synthetic pathways for preparing a series of novel metal porphyrins and metal phthalocyanines. These novel complexes will then be fabricated into organic nanomaterials through various noncovalent interactions including π-π interaction, hydrogen bonding, electrostatic, and metal-ligand coordination. Their self-assembly behaviors will be systematically investigated. We will focus on the research of two-photon absorption properties of these complexes and reveal the relationship between nano structure and two-photon absorption properties. The project will provide a scientific basis on the design and synthesis of novel organic two-photon absorption nanomaterials based on tetrapyrrolic macrocyclic complexes with large two-photon absorption cross section. This research work is aimed to provide useful tools to the controlled synthesis of organic two-photon absorption materials, which will surely be helpful for further research and application of organic nanomaterials.

有机双光子吸收材料在三维光信息存储，光限幅，双光子动力学疗法和荧光显微成像等方面有着广泛的应用前景，制备优秀的有机双光子吸收材料是科学家面临的挑战。卟啉、酞菁分子具有高度共轭的分子结构、优异的光电磁等功能特性以及对光、热的高度稳定性，已成为极有潜力的新型双光子吸收材料。本项目将深入研究由卟啉、酞菁分子形成的纳米材料的双光子吸收性质。首先通过向卟啉、酞菁分子周边不同位置引入功能基团，向分子中心引入不同的金属离子等手段，对该类有机分子进行功能化修饰，进而通过分子间的非共价作用将其制备成有机纳米材料，研究这种有机纳米材料的结构、形貌，重点探究有机纳米材料的双光子吸收性质与纳米结构之间的构效关系，以实现通过有效的组装手段获得具有高双光子吸收截面的有机双光子吸收材料的目标，为设计制备性能优良的纳米双光子吸收材料和建立物质双光子吸收性质与结构关系模型提供理论和材料基础。

高效双光子吸收材料在许多现代高科技领域如三维微制作，双光子动力学疗法，双光子光限幅，三维光数据存储和荧光显微成像等方面都有重要的应用前景，基于双光子吸收过程的分子设计、组装及性能研究已经成为材料学和光电子领域的热门课题。卟啉、酞菁具有刚性的分子结构以及高度离域的π电子体系，表现出各不相同的电子特性，是极具潜力的双光子吸收材料。经过三年来的不懈努力，课题围绕开拓新型双光子吸收材料这一主题，以提高材科的非线性光学效应为导向，按计划进展顺利，各项研究任务得以落实和执行。本课题的主要研究成果包括：（1）利用卟啉、酞菁的多变性及易裁剪性，设计合成多个系列的卟啉、酞菁化合物，引入稠环芳烃（如萘基、菲基、芘基）、吸电子基团（如碘基）、给电子基团（如烷氧基）等功能基团，扩大卟啉的共轭体系，或构建donor-π-acceptor体系，实现对共轭大环分子电子结构的有效调控；（2）系统研究了取代基种类，数量，中心金属种类等对其双光子吸收性质的影响，总结规律;（3）通过分子间弱相互作用将共轭大环分子组装成具有理想结构的超分子纳米聚集体;（4）测试功能分子及其纳米聚集体的双光子吸收性质及光限幅性质，讨论了功能分子的结构及聚集方式对双光子吸收性质的影响。获得了一些具有重要理论意义的实验结果，为卟啉、酞菁类有机双光子吸收材料的制备提供了理论指导。在本项目的支持下共发表了11篇学术论文，全部为SCI收录论文，其中一区文章1篇，二区文章5篇。在国际国内形成了一定的影晌，推动了相关科学研究的发展。对具有应用价值的成果，申报专利4项。