Soft group 13/15 organic-inorganic hybrid materials

软族13/15有机-无机杂化材料

• 批准号: 235439324
• 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: Independent Junior Research Groups
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/235439324?language=en
• 关键词: Soft; group; 13; 15; organic

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.

本项目建议书由两部分组成，旨在开发在一个框架中包含有机结构单元和无机主族元素的π共轭杂化材料。第一部分的目的是制备新型的π共轭的线性聚合物，其衍生自成熟的半导体有机聚合物，如聚（对亚苯基亚乙烯基）（PPV）、聚乙炔（PA）或聚（对亚苯基）（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，这样的系统显示出扩展的π电子离域沿着主链。特别有趣的结构和电子效应，预计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。为了获得定义明确的材料，将开发新的和温和的合成程序，如开环聚合（ROP）以前未知的BN-和BP-桥连对环芳。该项目的第二部分是开发具有特定光学和电子性质的新型分子染料。目标体系是在类卟啉和亚类卟啉骨架的中位具有硼和氮或硼和磷中心的大环。这些物质被设计为具有大环共轭的芳香族18-或14-π电子系统。初步的含时密度泛函计算表明，这一概念可能导致材料具有潜在的有趣的物理性质。此外，还可能出现不寻常的协调能力。除了它们在有机光化学中的应用潜力外，获得新的大环化合物可能有助于回答基本问题，例如在多大程度上不同的主族元素可以通过扩展的π系统进行通信，特别是在大环共轭卟啉或subporphyrinoid框架内。

项目成果

Borazine-based inorganic–organic hybrid cyclomatrix microspheres by silicon/boron exchange precipitation polycondensation

• DOI: 10.1039/c7py01006k
• 发表时间: 2017-09
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: N. Riensch;Ayse Deniz;Sebastian Kühl;L. Müller;A. Adams;A. Pich;Holger Helten

Poly(iminoborane)s: An Elusive Class of Main-Group Polymers?

• DOI: 10.1002/anie.201607131
• 发表时间: 2016-10-10
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Ayhan, Ozan;Eckert, Thomas;Helten, Holger
• 通讯作者: Helten, Holger