Synthetic Advances for Conjugated Material Synthesis

我们的研究重点是解决在共轭有机材料背景下提出的合成挑战。这些材料将取得重大技术突破，使光伏、发光二极管和场效应管等灵活、轻便、低成本的电子设备得以发展。创新的新合成能力将使设计新的分子结构成为可能。最终，这将导致这些新材料的性能增强，从而改善器件性能。该提案概述了为实现这些目标而开展的三个项目。 噻吩类化合物是共轭聚合物和小分子有机材料中最重要的一类化合物。本文提出了一种新的噻吩基材料的催化合成与聚合方法。该方法应该改进现有的方法，并提供互补的反应性，从而方便地组装新型的基于噻吩基的聚合物材料。 联芳基序广泛存在于各种化学领域，是共轭有机材料的普遍特征。虽然传统的交叉偶联反应被证明是有用的合成工具，但直接C-H键芳基化最近已成为一种更有效的替代方法。然而，要使直接芳基化成为真正广泛的合成用途，仍有许多缺点需要解决。在这里，我们建议设计催化剂/配体结构，特别是通过使用最近出现的一个机械框架作为催化剂设计的指南来解决其中的一些挑战。 聚对苯撑乙烯-S(PPV)是一类最早被用于尖端有机电子应用的共轭聚合物，但仍处于相对未开发的状态。这在很大程度上是由于PPV型聚合物的合成可及性有限，这不仅阻碍了新衍生物的设计和测试，还限制了可合成聚合物的现有性能。在这里，我们提出了一种利用C-H键作为合成手柄并利用过渡金属催化的氢芳基化反应来合成PPV型共轭聚合物的替代方法。考虑到所需的简单单体，它的原子经济性以及合成其他难以获得的聚合结构的能力，新的聚合反应应该被证明是有价值的。 我们还概述了拟议的合成进展将为高效构建大型功能共轭有机材料库提供机会。这项研究计划的长期目标包括利用合成技术获得以前无法获得的共轭材料，以便在各种令人兴奋的有机电子应用中进行筛选。

Our research is focused on tackling synthetic challenges posed in the context of conjugated organic materials. These materials are poised to make significant technological breakthroughs that will enable the advancement of flexible, lightweight, low-cost electronic devices such as photovoltaics, light emitting diodes and field-effect transistors. Innovative new synthetic capabilities will allow the design of novel molecular architectures. Ultimately, this will lead to enhanced properties for these new materials and, therefore, improved device performances. This proposal outlines three projects in pursuit of these goals. Thiophenes represent one of the most important classes of compounds found in both conjugated polymer and small molecule organic materials. Herein, a new catalytic thiophene synthesis and polymerization for thiophene-based materials is proposed. The method should improve upon and provide complimentary reactivity to, existing methods allowing for the expedient assembly of novel thiophene-based polymeric materials. The biaryl motif is heavily in a variety of chemical fields and is a prevalent feature of conjugated organic materials. While traditional cross-coupling reactions prove useful synthetic tools, direct C-H bond arylation has recently emerged as a more efficient alternative. However, many drawbacks remain to be solved for direct arylation to become of truly broad synthetic utility. Herein, we propose designing catalyst/ligand structures specifically meant to solve some of these challenges by using a recent emerging mechanistic framework as a guide to catalyst design. Poly(p-phenylene vinylene)s (PPV) are a class of conjugated polymers which were among the first to be utilized for cutting-edge organic electronic applications and yet remain relatively unexploited. This is due in large part to limited synthetic accessibility of PPV-type polymers which not only hampers the design and testing of new derivatives but also restricts available properties of synthetically attainable polymers. Herein, we propose an alternative approach to PPV-type conjugated polymers by utilizing the C-H bond as a synthetic handle and exploiting transition-metal-catalyzed hydroarylation reactivity. The new polymerization reaction should prove valuable given the simple monomers required, its atom economical nature and ability to synthesize otherwise inaccessible polymeric structures. We also outline the opportunity that the proposed synthetic advances will provide an opportunity for the efficient construction of large libraries of functional conjugated organic materials. Long-term goals of this research program include utilizing the synthetic techniques to obtain previously inaccessible conjugated materials to be screened in a variety of exciting organic electronic applications.