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

康涅狄格大学材料科学研究所的Gregory A. Sotzing教授受到有机和大分子化学计划的支持，研究用于制备共轭聚合物的熔融五元自行车的聚合。在这些单体中有三个聚合位点，可以对不同连接的线性共轭聚合物进行严格的研究。Sotzing教授建议分别阻断融合自行车的每个α位点，以制备区域不规则和区域规则聚合物。对词形差异的研究将是有重大价值的。例如，通过熔融五元自行车的两个位置的聚合将产生包含锁定的顺曲面构象的线性共轭聚合物，而通过同一单体上的两个不同位置的聚合将产生包含唯一锁定的反曲面构象的线性共轭聚合物。区域规则性对聚合物光学和电子性能的影响也将被探讨。由于多种共轭途径和三个α位点的几何位置，这些熔融自行车将用于制备新型共轭大环，可能用于分子导体，金上的分子有序和金属结合应用。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）与他的固态交联程序相结合，作为生成共轭聚合物纳米线的方法。本研究将涉及耦合过程的基本检查，因为它涉及前驱体聚合物结构，聚合物膨胀和氧化电位。在有机和大分子化学项目的支持下，Sotzing教授将有助于理解所研究材料中不同的共轭途径，并确定是否本然电导率可以通过分支点的多个途径存在。这可能会导致未来的发展和对分子电子学的更好理解。通过书写导电聚合物纳米线和理解这种新的书写技术，这项研究可以在未来为纳米模式光电子和其他纳米级器件（如晶体管和传感器）带来工具。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一个卓越的应用中心AFRL联系在一起，将为研究生和本科生营造一个学习和创造的环境。在提议的期限内，电子鼻实验将被纳入高中实验课程，以便在电子设备领域教育中学水平的学生，以及传感器如何成为国土安全的重要组成部分。这个项目将让高中生更广泛地了解化学是如何在基本层面上与技术密切相关的。

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.