Soft group 13/15 organic-inorganic hybrid materials

该项目提案包括两个部分，旨在开发包含有机构建块和无机主族元素的pi共轭杂化材料。第一部分的目的是制备新型的π共轭线性聚合物，这些聚合物来源于已建立的半导体有机聚合物，如聚对苯基乙烯（PPV），聚乙炔（PA）或聚对苯基乙烯（PPP），其中主链的特定C-C单元被等电子B-N或B-P单元取代。初步的计算研究预测，这种体系沿主链呈现出延伸的pi-电子离域。特别有趣的结构和电子效应有望在由不同芳香性的杂环组成的聚合物中观察到。为了获得定义良好的材料，新的和温和的合成方法将被开发，如开环聚合（ROP）以前未知的BN-和bp桥接的副环环烷。它将试图产生活性聚合系统，从而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。该项目的第二部分的目标是开发具有专门定制的光学和电子特性的新型分子染料。靶系统是在类卟啉和亚类卟啉框架的介孔位置具有硼和氮或硼和磷中心的大环。这些物种被设计成具有大环共轭，芳香18-或14-pi电子系统。初步的时间相关DFT计算表明，这一概念可能导致具有潜在有趣的光物理性质的材料。此外，可能会出现不寻常的协调能力。除了它们在有机光伏中的应用潜力之外，获得新的大环可能有助于回答一些基本问题，例如不同的主族元素在扩展pi系统上的通信程度，特别是在大环共轭卟啉类或亚卟啉类框架内。

This project proposal consists of two parts aimed at the development of pi-conjugated hybrid materials containing organic building blocks and inorganic main group elements in one framework. The objective of the first part is the preparation of novel pi-conjugated, linear polymers derived from well-established semiconducting organic polymers such as poly(p-phenylenevinylene) (PPV), polyacetylene (PA), or poly(p-phenylene) (PPP), in which specific C-C units of the backbone are replaced by isoelectronic B-N or B-P units. Preliminary computational studies predict that such systems show extended pi-electron delocalization along the main chain. Particularly interesting structural and electronic effects are expected to be observed with polymers consisting of alternating heterocyclic building blocks of different aromaticity. In order to obtain well-defined materials, new and mild synthetic procedures will be developed such as ring-opening polymerizations (ROP) of previously unknown BN- and BP-bridged paracyclophanes. It will be attempted to generate living polymerization systems, which enable precise control over polymer architecture and offer the possibility to prepare block copolymers with potential for nanoscience applications.The aim of the second part of this project is to develop novel molecular dyes with specifically tailored optical and electronic properties. Target systems are macrocycles having boron and nitrogen or boron and phosphorus centers in the meso positions of porphyrinoid and subporphyrinoid frameworks. These species are designed to feature a macrocyclic conjugated, aromatic 18- or 14-pi-electron system. Preliminary Time-Dependent DFT calculations reveal that this concept may lead to materials with potentially intriguing photophysical properties. Furthermore, unusual coordination abilities may arise. In addition to their potential for application in organic photovoltaics, gaining access to the novel macrocycles may help to answer fundamental questions such as to what extent can different main group elements communicate over extended pi systems, in particular, within a macrocyclic conjugated porphyrinoid or subporphyrinoid framework.