基于卟啉类星型功能分子设计、合成和性质研究

The porphyrin and its derivatives have a unique electronic structure and photoelectric properties, and have a wide application prospect in the field of solar cells, optoelectronic devices, and simulated organisms photosynthesis, etc. In this project the applicants intend to describe the strategy toward novel star-shaped dyes containing porphyrin with a central truxene and porphyrins, corroles, fullerences or Difluoroborondipyrromethene (BODIPY) arms. A seies of novel star-shaped asymmetrical chromophores with donor-acceptor will be synthesized by use of truxene as the bridge to directly connect the truxene core embedded within the porphyrins and other different chromophores such as fullence, corrole and BODIPY，such as porphyrin-truxene-corrole-fullence molecular system.This is the first time that three different chromophores (porphyrins, corroles, fullerences or BODIPYS) are linked into the same truxene choromphore molecule. The introduction of electron deficient or electron-rich substituents in the periphery of the porphyrin ring adjusts the photophysical properties of the synthesized compounds. The structural characterization and properties of the star-shaped compounds are studied with a variety of spectroscopic and electrochemical techniques. Our important focuses are on the intramolecular photoinduced energy and electron-transfer processes between the donor and the acceptor; the effect of the different chromophores and the number and location of the substituent species in the star-shaped molecule on the photophysical properties will be systematically investigated by use of the experiment and theoretical calculation of quantum chemistry. The relationship between the molecular structure and photophysical properties will also be studied. In addition, the impact of different solvents on the photoinduced energy transfer and electron transfer process will be explored. Finally, we will study the structures and their physical and chemical properties of star-shaped compounds with efficient energy transfer and long-lived electron-transfer state and provide a important theoretical basis and experimental evidence for the directed synthesis and potential application as molecular devices such as photovoltaic cells, field effect transistors,etc. of this family of the compounds in the future.

卟啉及其衍生物具有独特的电子结构和光电性能，在太阳能电池、光电子器件以及模拟生物体光合作用等方面都有着广泛的应用前景。本项目以三聚茚（truxen）为核，以卟啉、咔咯、富勒烯及BODIPY为臂，合成一系列三聚茚直接桥连卟啉及其他两个不同生色团的具有给体-受体的新型不对称星型分子，如卟啉-三聚茚-咔咯-富勒烯四元体系等；并在卟啉环或咔咯环中引入给电子或吸电子取代基以调控化合物的光物理性质。以实验和量子化学理论计算相结合的方式，研究不同发色团和取代基种类、数目和位置对分子光物理性质的影响，探索分子内给体和受体间光致能量转移和电子转移机理，研究分子结构与光物理性能的构效关系，研究不同溶剂对能量转移和电子转移的影响，研究具有高效能量转移和长寿命电荷分离态的星型化合物所具有的结构和性质，为该类化合物的定向合成及作为光伏电池、场效应晶体管等分子器件的潜在应用提供重要的理论基础和验依据。

光诱导能量/电子转移在光化学反应、太阳能利用、光合作用机理等方面起着重要作用。星型化合物具有星射型结构，便于控制分子内的相互作用，具有独立优化的物理性质和光电性质且能成功抑制激基复合物的生成。本项目以三聚茚（truxen）为核，合成一系列具有给体-受体的新型不对称星型分子。.以1-茚酮为原料合成三聚茚，并以三聚茚为核合成了富勒烯-三聚茚-卟啉、富勒烯-三聚茚-BODIPY、富勒烯-三聚茚-咔咯、BODIPY-三聚茚-卟啉、BODIPY-聚茚-咔咯、卟啉-三聚茚-咔咯等多个具有给体/受体的星型三基元分子体系。采用1HNMR、13C NMR、高分辨质谱等分析手段对所得化合物的结构进行了鉴定, 并研究了它们的紫外吸收光谱、稳态荧光光谱及光稳定性等光物理性质。结果表明:这些星型分子体系均能发生能量/电子转移，具有良好的光物理性质。.合成了富勒烯-三聚茚-咔咯-BODIPY、富勒烯-三聚茚-BODIPY-卟啉、富勒烯-三聚茚-卟啉-咔咯等多个具有给体-受体的四基元星型分子体系。对所得化合物的结构进行了表征,它们的光物理物质研究表明：各个功能基团与三聚茚之间仅存在弱的相互作用，并能发生有效的能量及电子转移。.利用wittig反应及Suzuki反应合成了4个含有香豆素基给体-受体的星型分子。对合成化合物的结构进行了表征, 并研究了它们的光物理性质。研究结果表明：三聚茚与香豆素形成了有效的共轭作用，导致其吸收光谱和荧光光谱发生了显著的红移；这些星型分子体系同样存着能量/电子转移过程，显现出优良的光物理性质。.将含醛基的三聚茚衍生物与BODIPY的3位和5位甲基进行缩合，得到了8种结构新颖三聚茚修饰的红外/近红外BODIPY 荧光染料分子。采用1HNMR、13C NMR、高分辨质谱等分析手段对合成所得的化合物的结构进行了表征，研究了它们的光物理性质。结果表明：在BODIPY的3位引入一个三聚茚共轭基时，电子吸收和荧光光谱波长在600 nm以上；而在BODIPY的3、5位同时引入三聚茚共轭基时，电子吸收和荧光光谱波长在650 nm以上。另外，在BODIPY 3、5位共轭的三聚茚基团引入不同基团对其光物理性质几乎未有影响。.本课题的研究为实现太阳能的高效转化与存储、设计和制备性能优越的分子光电材料及实际应用提供了重要的实验基础和理论依据。