Expanded Porphyrins and Other Synthetic Polypyrrole Macrocycles

本更新项目的重点是扩展卟啉和相关的聚吡咯大环的化学。重点将放在可能i)表现出不寻常的阳离子配位性质，ii)表现出液晶行为，或iii)表现出有趣的理论，光谱或光学性质的化合物上。这项工作有望进一步深入了解控制聚吡咯大环化学的基本“基本规则”，即如何将固有的结构性质，如大环的大小、形状和芳香性（或缺乏芳香性）转化为可观察的化学特征，包括底物识别选择性、金属配合物稳定性和液态结晶度。新的合成方法，包括基于氧化偶联、硫桥接和氮连接的方法，将被开发出来，以补充已知的方法，如Heck偶联和烯烃复分解，这些方法在扩展卟啉或低聚吡啶大环领域尚未受到太多关注。有了这个更新奖，有机和大分子化学项目正在支持德克萨斯大学奥斯汀分校化学和生物化学系的乔纳森·l·塞斯勒教授的研究。Sessler教授正在探索与所谓的卟啉单位有关的新型有机化合物的合成方法，卟啉单位构成了氧气运输和储存蛋白质、血红蛋白和肌红蛋白的基础。由此产生的系统有望产生新的催化剂、传感器和光调制器件。合成卟啉类似物领域的工作是高度跨学科的，涉及有机合成、无机配位化学、光谱学、光学、材料科学、催化和理论分析等方面。因此，它为年轻的研究人员提供了良好的培训，使他们能够在各种研究环境中有效地工作，包括学术界、工业界和政府。这一领域的工作也直接有助于我们技术基础设施的发展。

This renewal project is focused on the chemistry of expanded porphyrins and related polypyrrolic macrocycles. Emphasis will be placed on compounds that are likely to i) demonstrate unusual cation coordinating properties, ii) show liquid crystalline behavior, or iii) display interesting theoretical, spectroscopic, or optical properties. The proposed work is expected to provide further insights into the basic "ground rules" that govern the chemistry of polypyrrole macrocycles, namely how are intrinsic structural properties, such as macrocycle size, shape, and aromaticity (or lack thereof), translated into observable chemical features, including substrate recognition selectivity, metal complex stability, and liquid crystallinity. New synthetic methods, including those based on oxidative coupling, sulfur bridging, and nitrogen linking, will be developed to complement known methodologies, such as Heck couplings and olefin metathesis, that have yet to receive much attention in the expanded porphyrin or oligopyrrole macrocycle areas.With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Jonathon L. Sessler, of the Department of Chemistry and Biochemistry at the University of Texas at Austin. Professor Sessler is exploring methods for the synthesis of novel organic compounds related to the so-called porphyrin unit that forms the basis of the oxygen transport and storage proteins, hemoglobin and myoglobin. The resulting systems are expected to give rise to new catalysts, sensors, and light modulating devices. Work in the synthetic porphyrin analogue area is highly interdisciplinary, involving aspects of organic synthesis, inorganic coordination chemistry, spectroscopy, optics, materials science, catalysis, and theoretical analysis. It thus provides an excellent training for young researchers who are then able to work effectively in a variety of research settings, including academe, industry, and government. Work in this area also contributes directly to the development of our technological infrastructure.