共轭有机光电材料的合成方法及其性能研究

Π-conjugated polymers or small molecules are the primary materials for organic electronics. This project will focus on studying the synthetic methodology for such materials. During our research on the synthesis of π-conjugated materials, two aspects, including the optimization of current methods and the exploration of better alternatives to the traditional ones, will be considered. So, the following issues will be studied in details in this resaerch project. First, conjugated polymers synthesized via C?C couplings such as Suzuki reactions are traditionally catalyzed by soluble homogeneous ligated palladiums, which suffer the complicated side reactions and high contamination of residual catalysts. To overcome these drawbacks, the ligand-free heterogeneous Pd catalyst for the C?C coupling polycondensations will be developed in this project. Second, in order to make the synthetic process more straightforward and efficient, we will apply the method of direct arylation of C-H bonds (DACH) to synthesis π-conjugated optoelectronic materials. Third, both the DACH reaction and the classical C-C coupling have their advantages and shortcomings. So, in this project, the DACH reactions and the traditional C-C couplings will be used in combination. Such a combined strategy should make the synthesis of structurally novel and high performance π-conjugated materials much more facile and versatile. Fourth, to test the superiorities of these new synthetic methods, the device performances of the synthesized materials will be investigated in our study. It is well known that the synthetic methodology is the research focused on synthetic tools. An excellent synthetic tool should make the design and synthesis of π-conjugated materials much more diverse and low cost. Consequently, a larger scope of application of π-conjugated materials in the areas of new energy and information technology will be explored. Also, the process of commercialization of the π-conjugated materials will be accelerated. For the above reasons, this project, as a systematic study toward the synthetic methodology, will effectively prompt the highly-efficient, low-cost, green, and large-scale synthesis of organic optoelectronic materials.

Π-共轭型高分子或小分子是有机电子学的基础材料，本项目致力于该类材料的合成方法研究，分别从优化已有方法和探索新型方法两种角度出发，系统开展π-电子材料的合成研究。项目将：ⅰ）通过非均相催化偶联反应（Suzuki等）合成共轭聚合物，以克服传统均相体系存在的催化剂残余及副反应复杂等问题；ⅱ）利用具有高度原子经济性的C－H键直接芳基化（DACH）合成π-电子材料，使合成过程简捷高效；ⅲ）结合DACH反应与经典偶联反应的各自优势，联合使用两种方法，更高效地合成结构新颖、性能优越的π-电子材料；ⅳ）通过器件研究检验新型合成法的优越性。 合成方法学是对合成工具的研究，优越的合成工具将使π-电子材料的设计与合成更加灵活多元化及更为廉价，从而拓展其在新能源及信息技术领域的应用范围，加速其商业化进程。因此本项目的开展对于实现π-电子材料的高效、低成本、绿色及规模化制备具有重要的促进作用。

π-共轭聚合物或小分子半导体材料已被广泛应用于各类有机电子器件，π-共轭有机功能材料的设计与合成是有机电子及其器件研究的基础和创新源泉。发展原子经济、兼容性高、原料易得的高效反应对于共轭功能材料的深入研究及其规模化应用具有重要意义。本项目致力于共轭有机功能材料的设计、合成及其光电器件研究。在有机光电材料合成方法学、以及有机太阳电池光活性材料的设计与合成、及其器件性能研究等领域已形成较为系统的研究。 .主要包括：1）首次利用原子经济性的C-H键活化反应合成tri-DPP，并用于有机太阳电池及其大面积器件研究； 2）通过DACH反应合成了一系列基于芘环的链状或枝状的多核DPP寡聚物，并用于有机太阳电池器件研究；3）发展了首个具有互锁、结构刚性的三维非富勒烯有机太阳电池电子受体，该受体在电子亲和力、三维电子传输及电子迁移率方面是目前普遍使用的富勒烯衍生物的有效模拟；4）利用C-H键活化反应，发展了首个基于三维给体/聚合物受体的BHJ OPV；5）从三种简单的起始原料出发，仅通过两步反应，即高效率地获得了基于DPP的复杂结构寡聚物，并以其作为电子受体与廉价的P3HT给体材料构建非富勒烯BHJ OPV；8）发展了一种一步法、高效率合成高分子量π-共轭光电寡聚物的合成方法，所得寡聚物分子量从1500至3300不等，该方法具有显著的原子经济、步骤经济及低成本的优势。.项目执行期间，申请者发表的新型分子达34种，其中用于有机光伏器件研究的分子10余种，所使用领域包括有机太阳电池（OPV）给体材料以及非富勒烯受体材料。围绕本项目发表高水平论文8篇，获授权专利一项。其中Advanced Science (1篇), J. Mater. Chem. A (2篇), ACS Appl. Mater. Interfaces (1篇)，Organic Chemistry Frontiers (1篇), Nanotechnology (1篇)，Science China Chemistry (1篇)及Dyes and Pigments（1篇）。一项成果被Material views亮点报道并被遴选为Advanced Science封面文章，同时入选ESI高被引论文，一篇论文入选J. Mater. Chem. A 2014年度热点论文，近三年发表论文被引用达160次。