Conjugated Polymer Networks

在共轭大分子之间引入共轭交联可以得到具有最有趣的光学和电子特性的大分子网络。 然而，关于具有这种结构基序的明确定义的材料的合成和加工的知识基础非常有限。 因此，提出了一个研究计划，这是集中在设计，合成和探索明确的共轭聚合物网络。 本论文的主要研究内容包括聚对苯乙炔（PPE）和聚噻吩（PT）衍生物的合成和研究，以及各种潜在的应用领域。 设想的活动将集中在有机金属杂化材料，其中共轭大分子和金属之间的金属-配体相互作用允许共轭交联的可控形成。 这种通用框架是特别有吸引力的，因为它容易允许通过配体交换反应合成获得所需的目标材料，并且还允许适当的处理方案。 一方面，旨在直接利用作为聚合物主链的组成部分的官能团作为结合位点，例如PPE中包含的亚乙炔基部分。 后者与各种金属中心形成稳定的络合物，包括Pt（0）和Pt（0），这将形成共轭交联。 另一方面，设想还将特定配体位点整合到缀合聚合物中。 联吡啶部分，这是很容易整合到所考虑的聚合物和稳定的配合物与各种金属中心，代表一个说明性的例子。 该项目的研究重点是电荷传输特性、电导率和非线性光学响应，系统研究交联对新型材料的电子和物理性质的影响，为当前国际上共轭聚合物化学、材料科学和物理领域的研究提供新的思路。 预计它将提供坚定的答案的基本问题如何共轭交联可以方便地引入到这些材料中，而不损害其加工性，以及如何可以采用这种结构的基序，以影响材料的光学和电子特性，在一个有益的方式。 由于其示范性和基础性的特点，该研究有望为未来设计、合成和应用具有特殊和独特的光电性能的功能材料提供广泛的知识基础。 为了在本科和研究生阶段开发创新和刺激性课程，并试图将研究与教育相结合，拟议的研究与一些教育要素相补充。 后者与PI的研究活动密切相关，包括创造本科生研究机会，开发新的光和电功能聚合物尖端课程，以及开发开拓性的推广计划-“聚合物科学日”-与克利夫兰自然历史博物馆合作实施。 建议的举措补充了“常规”教学任务，并解决了创新和激励课程的发展。

It is expected that the introduction of conjugated cross-links between conjugated macromolecules can lead to macromolecular networks with most interesting optic and electronic characteristics. However, the knowledge base regarding the synthesis and processing of well-defined materials with this structural motif is very limited. Thus, a research program is proposed, which is focused on the design, synthesis and exploration of well-defined conjugated polymer networks. The proposed research addresses the synthesis and investigation of different classes of polymeric materials, including poly(p-phenylene ethynylene) (PPE_ and poly(thiophene) (PT) deriavatives, and various fields of potential applications. The envisioned activities will be focused on organometallic hybrid materials in which metal-ligand interactions between the conjugated macromolecules and metals allow the controlled formation of conjugated cross-links. This general framework is particularly attractive, since it readily permits synthetic access to the desired target materials through ligand-exchange reactions and also allows for adequated processing schemes. On the one hand, it is intended to directly utilize functionalities that are integral part of the polymer backbones as binding sites, such as the ethynylene moieties comprised in the PPE. The latter form stable complexes with a variety of metal centers, including Pt(0) and Pt(0), which will form the conjugated cross-links. On the other hand, it is envisioned to also integrate specific ligand sites into the conjugated polymer. Bipyridine moieties, which are readily integrated into the polymers under consideration and from stable complexes with a variety of metal centers, represent an illustrative example. Initially focusing on charge-transport characteristics, electrical conductivity and nonlinear optic response, it is planned to systematically investigate the influence which the cross-links exert on the electronic and photophysical properties of the novel materials.The research in this proposal contributes new and original ideas to the current international effort in the fields of chemistry, materials science, and physics of conjugated polymers. It is anticipated that it will provide firm answers to the fundamental questions how conjugated cross-links can be conveniently introduced into these materials without compromising their processability, and how this structural motif can be employed to influence the material's optic and electronic characteristics in a beneficial way. Because of the exemplary and fundamental character, the research is expected to provide a broad intellectual basis for the future design, synthesis and application of functional materials with unusual and unique optic and electronic properties. With the aim to develop innovative and stimulating curricula at undergraduate and graduate level and in an attempt to integrate research and education, the proposed research is complemented with a number of educational elements. The latter are intimately related to the research activities of the PI and include the creation of undergraduate research opportunities, the development of a new cutting-edge course on photo- and electrofunctional polymers, and the development of a pioneering outreach program - the 'Polymer Science Days' - which is implemented in collaboration with the Cleveland Museum of Natural History. The proposed initiatives complement 'routine' teaching assignments and address the development of innovative and stimulating curricula.