Chen Shiyan, Feng Lingwei, Peng Lixia, Gao Xiang, Zhu Yongfa, Yang Liulin, Chen Dafa, Zhang Kai, Guo Xugang, Huang Fei, Xia Haiping
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202305489. doi: 10.1002/anie.202305489. Epub 2023 Jun 29.
The development of conjugated polymers especially n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks. Herein, a strong acceptor building block with di-metallaaromatic structure was designed and synthesized by connecting two electron-deficient metallaaromatic units through a π-conjugated bridge. Then, a double-monomer polymerization methodology was developed for inserting it into conjugated polymer scaffolds to yield metallopolymers. The isolated well-defined model oligomers indicated polymer structures. Kinetic studies based on nuclear magnetic resonance and ultraviolet-visible spectroscopies shed light on the polymerization process. Interestingly, the resulted metallopolymers with d -p conjugations are very promising electron transport layer materials which can boost photovoltaic performance of an organic solar cell, with power conversion efficiency up to 18.28 % based on the PM6 : EH-HD-4F non-fullerene system. This work not only provides a facile route to construct metallaaromatic conjugated polymers with various functional groups, but also discovers their potential applications for the first time.
共轭聚合物尤其是n型聚合物半导体的发展，得益于缺电子结构单元的设计与合成。在此，通过一个π共轭桥连接两个缺电子金属芳族单元，设计并合成了一种具有双金属芳族结构的强受体结构单元。然后，开发了一种双单体聚合方法，将其插入共轭聚合物骨架中以制备金属聚合物。分离得到的结构明确的模型低聚物表明了聚合物结构。基于核磁共振和紫外可见光谱的动力学研究揭示了聚合过程。有趣的是，所得具有d -p共轭的金属聚合物是非常有前景的电子传输层材料，可提高有机太阳能电池的光伏性能，基于PM6 : EH-HD-4F非富勒烯体系的功率转换效率高达18.28%。这项工作不仅为构建具有各种官能团的金属芳族共轭聚合物提供了一条简便途径，还首次发现了它们的潜在应用。
