稳定的Z-形分子的设计与合成

Z-shaped molecule refers to a type of polycyclic hydrocarbons with the Z-shape molecule structure, which are of fundamental interest and have potential applications in materials science. However, the inherent high reactivity and low stability make their synthesis and characterization very challenging. Z-shaped molecules can be prepared with low yield through traditional methods such as transannular cyclizations from dehydroannulene species and palladium-catalyzed cyclodimerization, which are not feasible for the synthesis of high-order Z-shaped molecules. In this proposal, a series of novel Z-shaped molecules are designed in which strong electron-withdrawing groups including isoquinoline, naphthothiadiazole and naphthalimide moieties are introduced in order to construct stable Z-shaped molecules. Based on this, the photophysical properties, electrochemical properties, ground state electron states and charge transporting properties will be studied systematically. Furthermore, the performances of Z-shaped molecules will be investigated as two-photo absorption chromophores, near-infrared dyes and field-effect transistors. This research will provide acomprehensive and systematical approachs to investigate the practical applications of Z-shaped molecules and their derivatives.

Z-形分子是指一类呈“Z”字母形状的稠环芳烃化合物，在材料学领域具有重要的理论研究价值和广阔的应用前景；然而，Z-形分子的稳定性较差、反应活性高，合成和表征非常具有挑战性。传统的Z-形分子合成方法跨环成环和钯催化二聚体缩合成环等，合成产率低，难以制备高阶Z-形分子。本项目设计了一系列新颖的Z-形分子，在分子的两端及湾区引入强吸电子的杂环结构单元，如异喹啉、萘并噻唑、萘酰亚胺等取代基，以构建结构多样的稳定的Z-形分子。在此基础上，我们将系统的研究Z-形分子的光物理性质、电化学性质、基态电子结构、电荷传输特性。更进一步，我们将研究Z-形分子在双光子吸收、有机近红外染料、场效应晶体管材料领域的应用性能。该研究将为Z-形分子及其衍生物的实用化提供深入而系统的研究思路。

基于有机电子学的新原理开发新颖的有机半导体材料仍然是当前该领域的研究重点和热点，围绕Z-形分子等含自由基光电材料主题开展了项目研究。我们首次发现并报道几乎所有的窄带隙的有机共轭小分子具有自由电子，揭示有机光电材料的自由基与有机光电材料的构效关系，（JPCC, 2017, 121,8579-8588）。针对Z-形分子等自由电子特征与性能关系开展研究，取得一系列颇具特色和创新性的研究成果。在近三年的独立科研工作中，以第一/通讯作者发表SCI论文30余篇，发表论文进入高被引论文3篇，受邀封面论文6篇，申请发明专利12项，授权8项。1）开发了一系列稳定的含自由基光电材料，代表性工作包括以下申请人为通讯作者的论文：Advanced Energy Materials, 2017, 7, 1601499；Journal of Power Sources, 2017, 358, 29-38；ACS Applied Materials & Interfaces, 2015, 7, 26405-26413等共计6篇一区SCI论文。 2) 创新性的研究并报道含自由基的共轭酚有机光电材料，用作空穴传输材料和阳极界面工程（JMCA, 2015, 3, 21537- 21544；JMCC, 2016, 4, 5297-5306；JMCC, 2016, 4, 8077-8085；ACS Appl. Mater. Interfaces, 2016, 8, 12377-12383）。3) 开拓了含有自由基的醇溶性的自掺杂有机光电材料体系，初步建立了“苯酚基有机电子材料学”的这一独特的研究方向（JMCA, 2017, 5, 3780-3785, Journal of Power Sources, 2017, 344, 160-167）。4) 开发了一系列高性能的掺杂态自由基的PEDOT光电材料，应用于有机光电器件（Journal of Materials Chemistry A, 2017, 5, 13817-13822等共计5篇论文）。