Supramolecular design of pi-electron functional materials

π电子功能材料的超分子设计

• 批准号: RGPIN-2018-06500
• 负责人: Perepichka, Dmitrii
• 金额: $ 6.85万
• 依托单位: McGill University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=713632
• 关键词: Supramolecular; design; pi; electron; functional

Design and synthesis of new pi-electron functional materials allows answering fundamental physical chemistry questions, and play an enabling role in a wide spectrum of applications from pigments and fluorescent labels, to semiconducting devices and electrochemical energy storage media. Our current understanding of optoelectronic properties of such materials is very advanced at the level of single molecules, but is rather limited in situations when the interaction of the molecules with each other and with interfaces are important. Our goal is to understand how electronic properties of organic matter arise and can be controlled at supramolecular level, and use this understanding to create novel types of semiconducting materials where an electronic conductivity arises as a result of programmable molecular self-assembly. This discovery grant will continuously involve 5 graduate students and w undergraduates in research towards this goal through the following short-term 4 projects/objectives. We will: 1) Develop novel dynamic covalent chemistry suitable for self-assembly of ordered pi-conjugated polymers and covalent organic frameworks (COFs) under thermodynamic equilibrium. Our first target is aldol cyclization of cyclic ketones leading to rigid conjugated systems with dipole-dipole stabilization. 2) Develop omniconjugated building blocks that provide efficient electronic communication in several direction (no “cross-conjugation”). This will be accomplished by the use of (i) sexitopic and (ii) stable pi-radicals “nodes”, which will used as monomers for highly conjugated COFs and as cores for star-shaped molecular materials. 3) Gaining control of electronic properties in organic semiconductors via complementary hydrogen bonding. Coassembly of p- and n-type semiconductors and electronic polarization due to H-bonding will lead to strong band-gap modulation (giving rise to intrinsic semiconductors) and can lead to conducting channels that can be turned-on by interaction with H-bonding complementary pairs (including biomolecules). 4) Understanding the role of external factors (other than molecular or crystal structure) in controlling the charge transport through organic semiconductors. This will have an immediate impact on the current field of organic field effect transistors (FET), and is a critical step for the future development of self-assembled electronic devices. The scientific impact of this work will be (a) new knowledge at the interface of organic chemistry and solid state physics, that will help stirring the current field of organic electronics along our long term vision and (b) novel electronically functional materials that will advance the current device technologies (FETs, solar cells), can enable novel applications, and will foster collaborations with materials physics and biochemistry groups.

新的Pi-Electron功能材料的设计和合成允许回答基本的物理化学问题，并在从颜料和荧光标签到半导体设备和电化学能量存储媒体的广泛应用中发挥了有效作用。我们目前对此类材料的光电特性的理解在单分子的水平上非常先进，但是当分子相互相互作用彼此以及与接口的相互作用时，在情况下相当有限。我们的目标是了解有机物的电子特性是如何产生的，并且可以在超分子水平上进行控制，并使用此理解来创建新型的半导体材料，其中由于可编程的分子自组装而产生电子电导率。 这项发现赠款将继续涉及5名研究生和W本科生通过以下短期4个项目/目标来研究这一目标。我们将： 1）开发新型的动态共价化学，适用于在热力学平衡下在有序的PI偶联聚合物和共价有机框架（COF）的自组装中。我们的第一个目标是对环状酮的藻环化，从而导致具有偶极偶极稳定的刚性共轭系统。 2）开发出量的构建块，这些构建块可在多个方向上提供有效的电子通信（无“交叉缀合”）。这将通过使用（i）六重和（ii）稳定的Pi-Radicals“节点”来实现，该节点将用作高度共轭COF的单体，以及作为星形分子材料的核心。 3）通过互补的氢键来控制有机半导体中电子性质的控制。由p和n型半导体和N型半导体和电子极化而导致的电子极化会导致强烈的带隙调制（产生固有半导体），并可能导致可以通过与H键完整成对（包括生物分子）相互作用来转动的通道。 4）了解外部因素（除分子或晶体结构以外）在控制通过有机半导体的电荷传输中的作用。这将对当前有机场效应晶体管（FET）的领域产生直接影响，并且是自组装电子设备未来发展的关键步骤。 这项工作的科学影响将是（a）在有机化学和固态物理学的界面上的新知识，这将有助于沿着我们的长期视觉激发当前的有机电子领域，以及（b）新颖的电子功能材料，这些材料将推动当前的设备技术（FETS，solar细胞），可以促进新颖的应用程序，并可以促进新颖的应用程序，并将与材料物理学和Biiochems and Interials Thress和Biiochems and Inality Change and Inality Changers and Inality Change促进合作。