Conjugated Halocarbon Chemistry for New Materials

这项研究计划研究不饱和卤代烃化合物的化学。考虑到它们的Lewis酸性和C-X键的一般反应性，共轭卤代碳化物，如卤化聚丁烯和卤代炔烃，为制造各种富碳材料提供了良好的起点。二碘多炔在有序晶体中的拓扑化学聚合将形成只由碳和碘组成的聚二乙炔。初步证据支持当二碘丁二炔和双(吡啶)主体分子的共晶在高压(3 Gpa)下形成这种聚合物。我们将研究这些前所未有的碘取代聚二乙炔的电子和光学性质，并探索它们向碘掺杂卡宾的转变。此外，还将开发二炔的区域选择性卤化和氢卤化方法，以制备卤化聚丁烯和卤化丁烯。实验将集中在控制加成的化学计量比和了解结构对反应区域化学的影响。进一步的研究将利用这些卤化聚烯和卤代炔的溶液相还原偶联来制备原本难以获得的聚合物，包括聚二乙炔、聚乙炔和聚并苯。更大的不饱和卤代烃，包括更长的二碘多烯和四碘文档烯，也将成为目标，突破已知的卤代烃化学的界限。通过这个奖项，有机和高分子化学计划支持纽约州立大学石溪分校化学系的南希·S·戈洛夫教授的研究。戈洛夫教授正在开发新的方法来制备具有特殊结构和化学组成的分子和聚合物。由于它们的电学和光学性质，这些材料将在半导体和非线性光学吸收方面得到应用。与无机材料相比，这种有机材料的重量更轻，更容易修改，价格也更低。新的合成方法对这一重要领域的发展至关重要。这项建议的一个主要组成部分涉及合作研究，增加跨国家和学科边界的沟通。该助学金资助的研究生和本科生将获得现代有机合成、计算模型、光谱学和聚合物表征方法方面的经验。他们将学习如何通过合作和在专业会议上展示他们的成果来交流科学。国际和平研究所表现出了将研究与教育相结合的坚定承诺，这一努力将继续进行拟议的研究。

This research program addresses the chemistry of unsaturated halocarbon compounds. Given their Lewis acidity and the general reactivity of C-X bonds, conjugated halocarbons such as halocumulenes and haloalkynes provide good starting points for making a large variety of carbon-rich materials. Topochemical polymerization of diiodopolyynes in ordered crystals will form polydiacetylenes made up only of carbon and iodine. Preliminary evidence supports formation of such polymers when cocrystals of diiodobutadiyne and bis(pyridyl) host molecules are subjected to high pressures (3 GPa). The electronic and optical properties of these unprecedented iodine-substituted polydiacetylenes will be examined, and their transformation into iodine-doped carbyne will be explored. In addition, methods will be developed for regioselective halogenation and hydrohalogenation of diynes to make halocumulenes and halobutenynes. Experiments will center on controlling the stoichiometry of addition and on understanding the influences of structure on the regiochemistry of reaction. Further studies will exploit the solution-phase reductive coupling of these halocumulenes and haloenynes to prepare otherwise inaccessible polymers, including polydiacetylenes, poly(ethynylacetylenes), and polyacenes. Larger unsaturated halocarbons, including longer diiodopolyynes and tetraiodocumulenes, will also be targeted, pushing the boundaries of known halocarbon chemistry.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Nancy S. Goroff, of the Department of Chemistry at SUNY - Stony Brook. Professor Goroff is developing new methods for the preparation of molecules and polymers with unusual architectures and chemical composition. Because of their electronic and optical properties, these materials will have applications as semiconductors and as non-linear optical absorbers. Such organic materials will be lighter in weight, more easily modifiable, and less expensive than their inorganic counterparts. New synthetic methods are critical to the development of this important field. A major component of this proposal involves collaborative research, increasing communication across national and disciplinary boundaries. The graduate students and undergraduates supported by this grant will gain experience in modern organic synthesis, computational modeling, spectroscopy, and polymer characterization methods. They will learn how to communicate about science by working together and by presenting their results at professional meetings. The PI has demonstrated a strong commitment to integrating research and education, an effort that will continue with the proposed research.