Conjugated Halocarbon Chemistry for New Materials

这个研究项目涉及不饱和卤代烃化合物的化学。考虑到它们的刘易斯酸性和C-X键的一般反应性，共轭卤烃如卤代枯烯和卤代炔为制备各种各样的富碳材料提供了良好的起点。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。初步证据支持形成这样的聚合物时，共晶体的二碘丁二炔和双（吡啶基）主机分子进行高压（3 GPa）。这些前所未有的碘取代的聚二乙炔的电子和光学性质将被检查，并将探讨其转化为碘掺杂的碳炔。此外，将开发用于二炔的区域选择性卤化和氢卤化以制备卤代枯烯和卤代丁烯炔的方法。实验将集中在控制化学计量的添加和理解的结构上的区域化学反应的影响。进一步的研究将利用这些卤代枯烯和卤代烯炔的液相还原偶联来制备否则难以获得的聚合物，包括聚二乙炔、聚（乙炔基乙炔）和聚并苯。更大的不饱和卤代烃，包括更长的二碘多炔和四碘多枯烯，也将成为目标，推动已知的卤代烃化学的边界。纽约州立大学斯托尼布鲁克分校化学系的戈罗夫说。 Goroff教授正在开发制备具有不寻常结构和化学组成的分子和聚合物的新方法。由于它们的电子和光学性质，这些材料将作为半导体和非线性光学吸收剂应用。这样的有机材料重量更轻，更容易修改，并且比无机材料更便宜。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，增加跨国家和学科界限的沟通。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结果来交流科学。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.