新型共价卟啉阵列一步合成法的构建及其光电性能研究

This project aims to develop a brand-new and simple, efficient and general protocol for the one step construction of novel covalently linked multiporphyrin arrays of good solubility and functionality through a simultaneous condensation-cyclization-polymerization reaction via novel monomers such as bis(dipyrromethanes). Firstly，we design and prepare a series of novel monomers and extend the synthetic method to a general protocol for synthesizing numerous kinds of monomers. Secondly，we design and prepare a series of novel porphyrin dimers via these obtained novel monomers and also extend the synthetic method to a general protocol for synthesizing numerous kinds of porphyrin dimers. Thirdly, we mainly study the methodology of the simultaneous condensation-cyclization-polymerization strategy for the one step construction of covalently linked multiporphyrin arrays, so as to successfully establish a brand-new protocol for synthesizing this kind of multiporphyrin arrays; and we prepare a series of functionalized multiporphyrin arrays of diverse structures by this brand-new and one step protocol. Lastly, we study the basic physical and chemical properties of all the novel compounds; and mainly study the influence of the molecular structure of multiporphyrin arrays on the photovoltaic efficiency of organic solar cells, with desire to exploit new-type organic solar cells of excellent properties and low costs. With the accomplishment of this project, we will realize the easy and efficient synthesis of multiporphyrin arrays only by one step, which will bring forth important innovations in theories and in methodologies for construction of multiporphyrin arrays; we will also acquire functionalized photoelectric materials of high stability and distinct performance, which will be provided with great scientific significance and application values in both advancing further studies and accelerating substantial utilization of functionalized photoelectric materials of multiporphyrin arrays.

本项目拟建立和发展一种全新的、且简洁高效谱适的共价卟啉阵列合成法，即通过各类新型双（二吡咯烷）等单体--缩合-环化-聚合一步法合成溶解性好的新型功能化卟啉阵列。本项目首先设计合成一系列新型单体并将其发展成具有一定普适性的合成方法；然后构建各类新型二聚卟啉并将其发展成适用性广的一步合成法；进而重点进行缩合环化聚合一步法合成共价卟啉阵列的研究，构建和实现卟啉阵列全新合成方法，并运用该方法设计合成一系列结构新颖的功能化卟啉阵列；研究其基础物理化学性质，重点研究卟啉阵列分子结构对有机太阳能电池光电性能的影响，以期开发性能优异、成本低廉的新型有机太阳能电池。本项目的完成，将实现卟啉阵列简捷高效的一步合成，对发展卟啉阵列合成方法学具有重要的理论和方法创新；同时可望获得性能优异的卟啉阵列光电功能材料，对推进和加速卟啉阵列光电功能材料的深入研究和实质性应用，具有重要的科学意义和应用价值。

针对聚卟啉合成非常困难的现实，本项目围绕新型卟啉阵列一步法合成的关键问题展开了系统的研究。确立了普适的各类新型双(二吡咯甲烷)及其衍生物单体的合成方法；运用该方法成功的合成了10多个系列40余种未见文献报道的双(二吡咯甲烷)及其衍生物单体；建立了新型二聚卟啉的一步法合成模型，掌握了各种因素对二聚卟啉的一步法合成的影响规律；运用该法成功的构建了10多个系列20多种新型二聚卟啉，并研究了其基本光电性质；探索了多聚卟啉的一步法合成策略；成功的合成了二吡咯甲烷及双(二吡咯甲烷)衍生物-BODIPY，测试了其光电化学性能，并制备有机太阳能电池器件测试了其光伏性能；揭示了其分子结构与集光性能和光伏性能之间的关系；培养了一种卟啉单晶，并对其结构进行精确的解析。. 本项目研究达到了预期的研究目标，超额完成了原定研究内容和任务，实现了原有研究方案，完成了年度研究计划，达成了预期研究结果，取得了一系列的创新性成果。已发表英文SCI论文4篇，还有一部分成果（3-5篇论文）待发表，培养研究生4名。