New Functional Materials via Self-Assembly and Catalysis

题为“通过自组装和催化的新功能材料”的提案将涵盖我们小组的两个不同研究领域，这些领域有可能产生有影响力的新基础科学以及具有有用特性和潜在社会意义应用的新型自组装和聚合材料。 1)自组装 目前的一个关键合成挑战涉及创建均匀和功能性的基于聚合物的1D纤维状和2D血小板颗粒，这些颗粒存在于纳米至微米的长度尺度上，用于各种应用。在这个提案中，我们概述了一个计划，以解决这个问题，利用和解决与生活结晶驱动的自组装平台相关的关键挑战。使用这种溶液加工种子生长方法，具有可结晶π-共辄嵌段和相关两亲物的两亲嵌段共聚物将用于可预测地构建具有受控尺寸和空间限定的化学性质的1D和2D电活性颗粒。我们今年早些时候发表的关于通过活性结晶驱动的自组装产生的1D共轭聚芴基颗粒的结果表明，通过光吸收形成的空穴-电子对或“激子”能够在所需的大距离（> 200 nm）上扩散，以允许产生足够厚度的光捕获膜，以吸收几乎所有的入射光。该扩散长度比通常发现的共轭聚合物的扩散长度大一个数量级。这些结果表明，由活性结晶驱动的自组装产生的粒子在例如具有提高效率的太阳能电池等光捕获光电器件中具有潜在的应用，我们的目标是探索这种令人兴奋的可能性。 2)催化 在过去的世纪中，过渡金属催化反应的发展使有机分子和聚合物的合成发生了革命性的变化。与此形成鲜明对比的是，用于创建基于主群元素的链式结构的合成方法仍然有限。我们的团队一直处于p-区元素之间键合的催化路线开发的最前沿，以促进主族分子和材料的改进路线的创建。在这项提案中，我们的目标是基于磷和其他p-嵌段元素的新型主族聚合物，这些聚合物具有一系列潜在的应用，一旦它们的特性被完全描述，这些应用将变得清晰。例如，随着卤化阻燃剂的逐步淘汰，新阻燃材料的开发是相关的，从这个角度来看，新的磷基p-区材料可能特别有前途。 拟议的研究旨在成为国际化学和材料科学的前沿。开发具有商业重要性的新产品的最终可能性是现实的，预计将对青年科学家进行出色和广泛的培训。

The proposal entitled “New Functional Materials via Self-Assembly and Catalysis” will cover two distinct areas of research in our group that have the potential to give rise to both impactful new fundamental science and also novel self-assembled and polymeric materials with useful properties and potential applications of societal relevance. 1) Self-Assembly A key current synthetic challenge involves the creation of uniform and functional polymer-based 1D fiber-like and 2D platelet particles that exist on a length-scale of nanometers to microns for various applications. In this proposal we outline a program to tackle this issue by exploiting, and addressing key challenges associated with, the living crystallization-driven self-assembly platform. Using this solution processing seeded-growth approach, amphiphilic block copolymers with crystallizable pi-conjugated blocks and related amphiphiles will be used to predictably construct 1D and 2D electroactive particles with controlled dimensions and spatially-defined chemistries. Our results published earlier this year for 1D conjugated polyfluorene-based particles created by living crystallization-driven self-assembly indicate that the hole-electron pairs or “excitons” formed by light-absorption are able to diffuse over the large distances needed (> 200 nm) to allow the creation of light-harvesting films of sufficient thickness to absorb virtually all of the incident light. This diffusion length is an order of magnitude larger than that normally found for conjugated polymers. The results indicate that particles created by living crystallization-driven self-assembly have potential applications in, for example, light-harvesting optoelectronic devices such as solar cells with improved efficiency and we aim to explore this exciting possibility. 2) Catalysis Over the past century the development of transition metal-catalyzed reactions has revolutionized the synthesis of organic molecules and polymers. In striking contrast, the synthetic methods used to create catenated structures based on main group elements are still limited. Our group has been at the forefront of the development of catalytic routes to bonds between p-block elements to facilitate the creation of improved routes to main group molecules and materials. In this proposal we target novel main group polymers based on phosphorus and other p-block elements with a range of potential applications which will become clear once their properties have been fully delineated. For example, with the phase-out of halogenated flame retardants, the development of new flame-retardant materials is pertinent and the new phosphorus-based p-block materials targeted may be particularly promising from this perspective. The proposed research aims to be at the leading edge of chemical and materials science internationally. The ultimate possibility of new commercially important products is realistic, and an excellent and broad training for young scientists is anticipated.