Conjugated group 13/15 inorganic-organic hybrid polymers

共轭基团 13/15 无机-有机杂化聚合物

• 批准号: 401739196
• 负责人: Professor Dr. Holger Helten
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/401739196?language=en
• 关键词: Conjugated; group; 13; 15; inorganic

In the last decades, conjugated polymers have been the subject of tremendous research activity due to applications in electronic and optoelectronic devices (OLEDs, OFETs, OPVs), for biomedical imaging, and sensory applications. In recent years, the focus has shifted towards the functionalization of conjugated polymers with inorganic main group elements. In particular, the incorporation of boron has led to novel hybrid macromolecules with intriguing properties and functions. The replacement of selected C=C units by their isoelectronic and isosteric B=N units in conjugated organic systems has emerged as a viable strategy to produce novel materials with structural similarities to their all-carbon congeners but in many cases fundamentally altered electronic features. This BN/CC isosterism approach has been particularly successfully applied to polycyclic aromatic hydrocarbons, but its application to polymer chemistry has only been scarcely explored. Furthermore, the incorporation of BP units, which are valence isoelectronic with BN and CC, into organic materials has been less well-studied, though the potential of the resulting BCP hybrid materials for electronic applications has been recognized quite recently. Polymers featuring BP linkages in the main chain are unknown thus far. The aim of this research proposal is the development of novel conjugated, cyclolinear polymers comprised of a backbone of organic building blocks and B=N or B=P units, respectively. Polymers with essentially linear B=N linkages are of particularly interest, as in such species possible conjugation along the polymer chain must occur through this unit because no alternative conjugation pathways exist. Exciting structural and electronic effects are expected to be observed also with polymers consisting of alternating heterocyclic building blocks of different aromaticity. The incorporation of electron-donor and -acceptor components via a modular approach will allow to effectively tune the electronic properties of the new materials. This will provide fundamental insight into the electronic interaction and communication over B=N and B=P units in linearly extended conjugated systems. In order to obtain well-defined materials, new controlled synthetic approaches to access such species under mild conditions, including (catalytic) AB type polycondensation and chain-growth routes. This may lead to living polymerization systems, which enable precise control over polymer architecture and offer the possibility to prepare block copolymers with potential for nanoscience applications.

在过去的几十年中，共轭聚合物由于在电子和光电器件（OLED、OFFEX、OPV）、用于生物医学成像和传感应用中的应用而成为巨大的研究活动的主题。近年来，研究的重点转向了无机主族元素对共轭聚合物的功能化。特别是，硼的掺入导致了具有有趣的性质和功能的新型混合大分子。在共轭有机体系中用等电子和等排的B=N单元取代选定的C=C单元已经成为一种可行的策略，以产生与其全碳同系物具有结构相似性但在许多情况下从根本上改变电子特征的新型材料。这种BN/CC电子等排方法已特别成功地应用于多环芳烃，但其应用于聚合物化学几乎没有探索。此外，BP单元，这是与BN和CC的价电子等电子的，到有机材料的掺入已较少研究，虽然所得BCP杂化材料的电子应用的潜力已经认识到相当最近。到目前为止，在主链中具有BP键的聚合物是未知的。本研究计划的目的是开发新型共轭的、环状线性的聚合物，其分别由有机结构单元和B=N或B=P单元的主链组成。具有基本上线性B=N键的聚合物是特别令人感兴趣的，因为在这样的物质中，可能的共轭沿着聚合物链必须通过该单元发生，因为不存在替代的共轭途径。令人兴奋的结构和电子效应，预计也将观察到与聚合物组成的交替杂环不同的芳香性的建筑块。通过模块化方法将电子供体和电子受体组分结合在一起将允许有效地调节新材料的电子性质。这将为线性扩展共轭体系中B=N和B=P单元上的电子相互作用和电子通信提供基本的见解。为了获得定义明确的材料，新的受控合成方法在温和条件下获得这些物种，包括（催化）AB型缩聚和链增长路线。这可能导致活性聚合系统，其能够精确控制聚合物结构，并提供制备具有纳米科学应用潜力的嵌段共聚物的可能性。