RUI: New Porphyrinoid Architectures with Extended Conjugation Pathways

RUI：具有扩展共轭途径的新型卟啉结构

• 批准号: 2247214
• 负责人: Timothy Lash
• 金额: $ 46.31万
• 依托单位: Board of Trustees of Illinois State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247214&HistoricalAwards=false
• 关键词: RUI; New; Porphyrinoid; Architectures; Extended

With support from the Chemical Synthesis program of the NSF Division of Chemistry, Professor Timothy Lash of Illinois State University is exploring the synthesis, characterization, and reactivity of compounds that resemble naturally occurring porphyrins. Metalated porphyrins are widespread in nature, e.g. hemes, and play crucial roles in photosynthesis and oxygen transport. Porphyrins also have numerous applications in a number of diverse areas, including materials science, catalysis, and medicine. Porphyrins have 4 nitrogen atoms within a central cavity that allow the structure to bind metal ions. However, an important class of related compounds, called carbaporphyrins, have a carbon atom in place of one of these nitrogens. Carbaporphyrins have modified properties that often complement those of naturally occurring porphyrins. The supported work is leading to the development of efficient routes to novel carbaporphyrins and related porphyrin-like systems that have unique reactivity and unusual properties. The results are increasing our understanding of fundamental chemistry concepts such as aromaticity, a fundamental property of molecules that leads to enhanced stability. Furthermore, structures of this type act as ligands to form stable complexes with important catalytic metals such as palladium and rhodium. Professor Lash and his students are studying applications of these metalloporphyrins in the preparation of fine chemicals. In addition, related such complexes are being explored for use as photosensitizers in photodynamic therapy. These projects are not only providing an excellent environment for training undergraduates and Masters level graduate students for careers in science, technology, engineering, and mathematics (STEM) but are also exposing these students to the multidisciplinary nature of modern scientific research.In this research, new synthetic routes to porphyrin-like systems are being developed, including methodology that makes use of cyclopropane dialdehydes. Applications of the “3 + 1” variant of the MacDonald reaction will provide structures having extended conjugation with alternative properties. For instance, porphyrin-like structures with fused aromatic rings, including phenanthrene, pyrene and acenaphthylene, will extend the platform and are expected to substantially alter the properties of these systems. Other examples of unique porphyrins include carboporphyrins hydroxyporphyrinoids, and tripyrrolic porphyrins. All these molecules have unique conjugation pathways and, as a result, interesting properties. The strategy to synthesize these substrates should be applicable to virtually all fused aromatic ring systems. These investigations are quite fundamental, providing access to important new porphyrinoid systems, and thus have the potential for major impact on the field of porphyrin chemistry.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在NSF化学司的化学合成计划的支持下，伊利诺伊州立大学的蒂莫西·拉什（Timothy Lash）教授正在探索类似于自然发生的卟啉的化合物的合成，表征和反应性。金属化的卟啉本质上是宽度的，例如hemes，并在光合作用和氧运输中扮演至关重要的角色。卟啉在许多潜水区域，包括材料科学，催化和医学，也有许多应用。卟啉在中央腔内具有4个氮原子，使结构结合金属离子。然而，一类重要的相关化合物，称为碳原子代替其中一种硝酸盐。碳碳纤维蛋白具有经常补充天然卟啉的特性。支持的工作导致发展具有独特反应性和异常特性的新型碳碳纤维蛋白和相关卟啉样系统的有效途径。结果正在增加我们对基本化学概念（例如芳香族）的理解，例如芳香族，这是分子的基本特性，导致稳定性增强。此外，这种类型的结构充当配体，形成具有重要催化金属（例如钯和若i的重要催化金属）的稳定络合物。 Lash教授和他的学生正在研究这些金属甲丁物的应用，以制备精细化学物质。此外，正在探索相关的复合物作为光动力疗法的光敏剂。这些项目不仅为培训本科生和硕士学位的研究生提供了一个绝佳的环境，从事科学，技术，工程和数学的职业（STEM），而且还将这些学生暴露于现代科学研究的多学科性质中。在这项研究，新的合成途径的新合成途径中，正在开发类似卟啉的系统的合成途径，包括使用Cyclopropane的方法，包括使用Cyclopropane的方法。麦克唐纳反应的“ 3 + 1”变体的应用将提供具有延长共轭的结构，并提供替代性能。例如，具有融合芳香环的卟啉样结构，包括苯鞭打，pyr烯和丙烯乙烯，将扩展平台，并有望大大改变这些系统的性质。独特的卟啉的其他例子包括甲状腺素羟基甲肾上腺素和三吡咯卟啉。所有这些分子都有独特的共轭途径，因此具有有趣的特性。合成这些基板的策略应适用于几乎所有融合的芳环系统。这些投资非常基本，可以访问重要的新卟啉系统，因此具有对卟啉化学领域的重大影响。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响标准通过评估来评估。