Conjugated Halocarbon Chemistry for New Materials

本研究计划探讨不饱和卤代烃化合物的化学性质。考虑到它们的刘易斯酸度和C-X键的一般反应性，共轭卤代烃，如卤代烯和卤代炔，为制造各种各样的富碳材料提供了良好的起点。在有序晶体中的二碘多炔的拓扑化学聚合将形成仅由碳和碘组成的聚二乙炔。初步证据表明，当二碘丁二炔和双（吡啶基）宿主分子的共晶受到高压（3gpa）时，会形成这种聚合物。研究了这些前所未有的碘取代聚二乙炔的电子和光学性质，并探讨了它们向碘掺杂碳炔的转变。此外，还将开发二炔的区域选择性卤化和氢卤化方法，以制备卤化烯和卤化丁烯。实验将集中在控制加成的化学计量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代烯烃和卤代烯烃的液相还原偶联来制备其他难以获得的聚合物，包括聚二乙炔、聚乙炔和聚丙烯腈。较大的不饱和卤代烃，包括较长的二碘聚醚和四聚乙烯，也将成为目标，突破已知卤代烃化学的界限。通过这个奖项，有机和大分子化学项目支持了纽约州立大学石溪分校化学系Nancy S. Goroff教授的研究。Goroff教授正在开发新的方法来制备具有不同寻常结构和化学成分的分子和聚合物。由于其电子和光学特性，这些材料将应用于半导体和非线性光学吸收剂。与无机材料相比，这种有机材料重量更轻，更容易修改，也更便宜。新的合成方法对这一重要领域的发展至关重要。该提案的一个主要组成部分涉及合作研究，增加跨国家和学科界限的交流。该基金资助的研究生和本科生将获得现代有机合成、计算建模、光谱学和聚合物表征方法的经验。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。PI已经表现出对整合研究和教育的坚定承诺，这一努力将在拟议的研究中继续下去。

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.