Carbaporphyrins and other highly modified porphyrinoid systems

本项目提出了一个深入的研究合成，表征和反应性的一些新的类卟啉大环。这些研究可能为卟啉型结构的性质（如芳香性）提供基本的见解，可能提供具有潜在有用性质的化合物（如光动力治疗应用的长波吸收性），并可能促进具有有趣和潜在有用催化性质的新型有机金属衍生物的制备。将开发碳卟啉和相关卟啉类化合物的改进路线。中-四芳基氮卟啉和苯并碳卟啉的直接合成途径已经允许合成新的有机金属衍生物，未来的研究将针对进一步的金属化反应和对类卟啉大环的修饰（例如，用二亚胺或四氧化锇）。新分子将通过光谱方法彻底表征，并在可能的情况下获得x射线晶体结构。这些新型碳卟啉类化合物的化学和光谱性质将为进一步了解卟啉型结构的芳香性质提供进一步的见解。从1,8-二羟基萘-2,7-二乙醛和1,10-菲罗啉-2,9-二乙醛制备进一步的修饰结构，这些大环很可能表现出有趣的配位化学。通过这个奖项，有机和大分子化学项目支持伊利诺伊州立大学的Timothy D. Lash教授，他的研究对杂环和有机金属化学领域具有重要意义，并可能导致催化和医学等多种应用。因此，这些项目不仅为培养有机合成领域的本科生和硕士研究生提供了良好的环境，而且使他们接触到现代科学研究的多学科性质。

This project proposes an in-depth investigation of the synthesis, characterization, and reactivity of a number of novel porphyrin-like macrocycles. It is suggested that these studies may provide fundamental insights into properties of porphyrin-type structures (e.g., aromaticity), may afford compounds with potentially useful properties (e.g., long wavelength absorbance for photodynamic therapy applications), and may facilitate the preparation of novel organometallic derivatives with interesting and potentially useful catalytic properties. Improved routes to carbaporphyrins and related porphyrinoids will be developed. Direct routes to meso-tetraarylazuliporphyrins and benzocarba-porphyrins have allowed the synthesis of novel organometallic derivatives, and future investigations will target further metalation reactions and modifications to the porphyrinoid macrocycle (e.g., with diimide or osmium tetroxide). The new molecules will be thoroughly characterized by spectroscopic methods and, where possible, X-ray crystal structures will be obtained. The chemistry and spectroscopic properties of these novel carbaporphyrinoids will provide further insights into the aromatic properties of porphyrin-type structures. Further modified structures will be prepared from 1,8-dihydroxy-naphthalene-2,7-dicarbaldehyde and 1,10-phenanthroline-2,9-dicarbaldehyde, and these macrocycles will most likely show interesting coordination chemistry.With this award, the Organic and Macromolecular Chemistry Program supports Professor Timothy D. Lash of Illinois State University whose research has important implications for the fields of heterocyclic and organometallic chemistry, and may lead to applications as diverse as catalysis and medicine. Hence, these projects not only provide an excellent environment for training undergraduates and MS level graduate students in the field of organic synthesis, but also expose them to the multidisciplinary nature of modern scientific research.