Conjugated group 13/15 inorganic-organic hybrid polymers

在过去的几十年里，由于共轭聚合物在电子和光电子器件（oled, ofet, opv），生物医学成像和感官应用中的应用，共轭聚合物已经成为大量研究活动的主题。近年来，无机主族元素共轭聚合物的功能化已成为研究的热点。特别是，硼的掺入导致了具有有趣性质和功能的新型杂化大分子。在共轭有机体系中，用等电子和等构B=N单元取代选定的C=C单元已成为一种可行的策略，可以生产与全碳同系物结构相似的新材料，但在许多情况下，电子特征从根本上改变了。这种BN/CC等构方法已特别成功地应用于多环芳烃，但其在聚合物化学中的应用还很少探索。此外，将BP单元（与BN和CC是价等电子）结合到有机材料中还没有得到很好的研究，尽管所得到的BCP杂化材料在电子应用方面的潜力最近已经得到了认可。在主链上具有BP键的聚合物迄今尚不为人所知。本研究计划的目的是开发新型共轭、环线型聚合物，这些聚合物分别由有机构建单元和B=N或B=P单元组成。具有基本线性B=N键的聚合物是特别感兴趣的，因为在这种物种中，沿着聚合物链的可能共轭必须通过该单元发生，因为没有其他共轭途径存在。由不同芳香性的杂环组成的聚合物也有望观察到令人兴奋的结构和电子效应。通过模块化方法结合电子供体和电子受体组件将允许有效地调整新材料的电子特性。这将为线性扩展共轭系统中B=N和B=P单位上的电子相互作用和通信提供基本的见解。为了获得定义明确的材料，新的受控合成方法可以在温和条件下获得这些物质，包括（催化）AB型缩聚和链式生长途径。这可能会导致活聚合系统，它可以精确控制聚合物的结构，并提供了制备具有纳米科学应用潜力的嵌段共聚物的可能性。

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.