CAREER: Novel Conjugated Macromolecules from Fused Heterocyclics and from Oxidative Solid-state Crosslinking

Gregory A.康涅狄格大学材料科学研究所的Sotzing得到了有机和大分子化学计划的支持，研究了用于制备共轭聚合物的稠合五元双环的聚合。在这些单体中具有三个聚合位点允许对不同连接的线性共轭聚合物进行严格的研究。Sotzing教授建议分别封闭稠合双环的每个α位点，以制备区域不规则和区域规则聚合物。对动词变位的差异进行研究将是一个重要的价值。例如，通过稠合五元双环的两个位置的聚合将产生含有锁定顺式构象的线性共辄聚合物，而通过相同单体上的两个不同位置的聚合将产生含有独特锁定反式构象的线性共辄聚合物。还将探讨区域规则性对聚合物光学和电子性质的影响。由于多个共轭途径和三个α位点的几何位置，这些稠合双环将用于制备新的共轭大环化合物，其可能用作分子导体、金上的分子有序化和金属结合应用。在另一项研究中，Sotzing教授将探索使用电化学原子力显微镜（ECAFM）结合他的固态交联过程作为生成共轭聚合物纳米线的方法。这项研究将涉及耦合过程的基本检查，因为它涉及到前体聚合物结构，聚合物溶胀和氧化电位。在有机和大分子化学项目的支持下，Sotzing教授将有助于了解所研究材料中的不同共轭途径，并确定是否可以通过分支点的多个途径存在固有导电性。这可能会导致未来的发展和更好地理解分子电子学。通过书写导电聚合物纳米线并理解这种新的书写技术，这项研究在未来可能会导致纳米图案光电子学和其他纳米级器件（如晶体管和传感器）的工具。合作研究将在空军研究实验室（AFRL）进行，研究光伏器件中的上述材料。这项高度跨学科的研究与卓越的应用中心AFRL联系在一起，将为研究生和本科生营造一个学习和创造力的环境。在拟议的时间内，电子鼻实验将被纳入高中实验室课程，以教育中学生电子设备领域的知识，以及传感器如何成为国土安全的重要组成部分。该项目将使高中生更广泛地了解化学如何在基础层面上与技术密切相关。

Professor Gregory A. Sotzing of the Institute of Materials Science at the University of Connecticut is supported by the Organic and Macromolecular Chemistry Program to study the polymerization of fused five-membered bicyclics for the preparation of conjugated polymers. Having three sites of polymerization within these monomers allows a rigorous study of differently linked linear conjugated polymers. Professor Sotzing proposes to separately block each one of the alpha sites of the fused bicyclics in order to prepare regio-irregular and regio-regular polymers. Of significant merit will be a study of the differences in conjugation. For example, polymerization through two positions of the fused five-membered bicyclics will produce linear conjugated polymers containing a locked cisoid conformation whereas polymerization through two different positions on the same monomer will produce linear conjugated polymers containing unique locked transoid conformations. The effect of regioregularity on the optical and electronic properties of the polymers will also be probed. Due to multiple conjugation pathways and the geometric locations of the three alpha sites, these fused bicyclics will be used for the preparation of novel conjugated macrocycles for possible use as molecular conductors, molecular ordering on gold, and metal binding applications. In a separate study, Professor Sotzing will explore the use of electrochemical atomic force microscopy (ECAFM) coupled to his solid-state crosslinking procedure as a method to generate conjugated polymer nanowires. This study will involve a fundamental examination of the coupling process as it pertains to precursor polymer structure, polymer swelling, and oxidation potential.With the support of the Organic and Macromolecular Chemistry Program Professor Sotzing will contribute to an understanding of different pathways for conjugation in the materials studied and determine if intrinsic conductivity can exist through multiple pathways of a branch point. This could lead to future developments and a better understanding of molecular electronics. By writing conductive polymer nanowires and understanding this new writing technique, the research could, in the future, lead toward tools to nanopattern optoelectronics and other nanoscale devices such as transistors and sensors. Collaborative research will be performed at the Air Force Research Laboratory (AFRL) studying the above-mentioned materials in photovoltaic devices. This highly interdisciplinary research tied to a center of excellence for applications, AFRL, will foster an environment of learning and creativity for both graduate and undergraduate students. Within the proposed period, electronic nose experiments will be incorporated into the high school laboratory curriculum in order to educate secondary level students in the field of electronic devices and how sensors are an essential component of homeland security. This project will give the high school students a broader understanding of how chemistry is intimately connected to technology on a fundamental level.