Conjugated Halocarbon Chemistry for New Materials

新材料的共轭卤碳​​化学

• 批准号: 0446749
• 负责人: Nancy Goroff
• 金额: $ 39.9万
• 依托单位: SUNY at Stony Brook
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-01-01 至 2008-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0446749&HistoricalAwards=false
• 关键词: Conjugated; Halocarbon; Chemistry; New; Materials

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.

该研究项目致力于不饱和卤化碳化合物的化学研究。考虑到其路易斯酸性和 C-X 键的一般反应性，共轭卤代碳（例如卤代积烯和卤代炔）为制造各种富碳材料提供了良好的起点。有序晶体中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。初步证据支持当二碘丁二炔和双(吡啶基)主体分子的共晶受到高压(3 GPa)时形成此类聚合物。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碳炔的转化。此外，还将开发二炔的区域选择性卤化和氢卤化以制备卤代积烯和卤代丁烯的方法。实验将集中于控制添加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积烯和卤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、聚乙炔基乙炔和多并苯。较大的不饱和卤化碳，包括较长的二碘多炔和四碘积烯，也将成为目标，从而突破已知卤化碳化学的界限。有机和高分子化学项目通过该奖项支持纽约州立大学石溪分校化学系 Nancy S. Goroff 教授的研究。 戈罗夫教授正在开发新方法来制备具有不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，这些材料将具有半导体和非线性光吸收器的应用。与无机材料相比，此类有机材料重量更轻、更容易改性且成本更低。新的合成方法对于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，加强跨国家和学科界限的交流。受此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方面的经验。他们将学习如何通过合作以及在专业会议上展示他们的成果来交流科学。 PI 表现出了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。