Fluorescent PN-Heterocycles in Supramolecular Chemistry and Recognition

超分子化学和识别中的荧光 PN 杂环

• 批准号: 2107425
• 负责人: Michael Haley
• 金额: $ 63万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2107425&HistoricalAwards=false
• 关键词: Fluorescent; PN; Heterocycles; Supramolecular; Chemistry

With the support from the Macromolecular, Supramolecular and Nanochemistry Program of the NSF Chemistry Division, Professors Michael Haley and Darren Johnson and their students at the University of Oregon will investigate a new class of molecules that contain adjacent phosphorous and nitrogen centers as part of overall structure. These "PN-heterocycles" feature a strong hydrogen bond donor adjacent to a strong acceptor within a compact, fluorescent core. Fundamental supramolecular chemistry is at the heart of this proposal, and our studies will explore and expand the utility of these easily-prepared molecules as fluorescent materials, strong hydrogen bonding motifs for self-assembly and molecular recognition, and supramolecular materials. This project provides interdisciplinary research training to graduate and undergraduate researchers. The broader impacts of this project also include (1) internship opportunities at universities, national labs, and companies, (2) individual development plans, (3) regional/international collaborations; and (4) mentoring opportunities to ensure students receive both a depth of technical training and a breadth of professional training to launch their careers. The PI's commitment to mentoring undergraduate research and to innovation suggests that the research will have broad impact.This fundamental research aims to design and synthesize PN-heterocycles as new fluorophores and as recognition motifs in supramolecular chemistry, organic materials, and molecule/ion recognition. The aims of this project are organized around the following two complementary primary objectives: (1) to perform fundamental studies on these PN-heterocycles in the areas of chiral resolution, organic materials, and new fused-arenes featuring extended conjugation and/or prototropic tautomerism; and (2) to explore the utility of PN-heterocycles in supramolecular chemistry in the areas of hydrogen bond-driven self-assembly, oxoanion recognition, and chiral recognition. The ultimate goal of this research program is to expand the fundamental understanding of these new PN-heterocycles and extend these studies into supramolecular chemistry and molecular recognition. These new heterocycles have the advantage of featuring a very strong hydrogen bonding motif with an inherently fluorescent scaffold, putting both chiral recognition and signal transduction elements directly at the site of recognition and assembly. This research employs a combination of methods, including calorimetric, NMR spectroscopic, and spectrophotometric titrations, to determine the binding properties of the supramolecular receptors and to gain a better understanding of how structural changes influence their binding affinity, selectivity, and optoelectronic properties. The studies provide the researchers with broad experience in organic synthesis, physical organic chemistry, supramolecular chemistry, computational chemistry, X-ray crystallography, and the interplay between electronic structure and molecular architecture.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化学部大分子、超分子和纳米化学项目的支持下，俄勒冈州大学的Michael Haley和Darren约翰逊教授及其学生将研究一类新的分子，这些分子包含相邻的磷和氮中心，作为整体结构的一部分。这些“PN-杂环”的特征在于在紧凑的荧光核内与强受体相邻的强氢键供体。基础超分子化学是这一提议的核心，我们的研究将探索和扩大这些容易制备的分子作为荧光材料、用于自组装和分子识别的强氢键基序以及超分子材料的效用。该项目为研究生和本科生研究人员提供跨学科的研究培训。该项目的更广泛影响还包括（1）在大学，国家实验室和公司的实习机会，（2）个人发展计划，（3）区域/国际合作;以及（4）指导机会，以确保学生获得技术培训的深度和专业培训的广度，以启动他们的职业生涯。PI对指导本科生研究和创新的承诺表明，该研究将产生广泛的影响。该基础研究旨在设计和合成PN-杂环作为新的荧光团和超分子化学，有机材料和分子/离子识别的识别基序。本项目主要围绕以下两个互补的主要目标展开：（1）对这些PN-杂环化合物在手性拆分、有机材料和具有扩展共轭和/或质子转移互变异构现象的新型稠合芳烃等领域进行基础研究;以及（2）探索PN-杂环在超分子化学中的应用，如氢键驱动的自组装，含氧阴离子识别，和手性识别。该研究计划的最终目标是扩大对这些新PN-杂环的基本理解，并将这些研究扩展到超分子化学和分子识别领域。这些新的杂环具有非常强的氢键基序与固有的荧光支架的特点，把手性识别和信号转导元件直接在识别和组装的网站。本研究采用了一种组合的方法，包括量热，NMR光谱和分光光度滴定，以确定超分子受体的结合特性，并获得更好的理解结构变化如何影响其结合亲和力，选择性和光电性能。这些研究为研究人员在有机合成、物理有机化学、超分子化学、计算化学、X射线晶体学以及电子结构和分子结构之间的相互作用方面提供了广泛的经验。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响评审标准进行评估，被认为值得支持。

项目成果

Impact of Internal Charge Transfer on the Photophysical Properties of Pyridine‐Fused Phosphorus‐Nitrogen Heterocycles

内部电荷转移对吡啶-熔融磷-氮杂环光物理性质的影响

• DOI: 10.1002/chem.202203918
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: McNeill, J. N.;Kascoutas, Melanie A.;Karas, Lucas J.;Zakharov, Lev N.;Wu, Judy I.;Johnson, Darren W.;Haley, Michael M.
• 通讯作者: Haley, Michael M.

Controlling Tautomerization in Pyridine‐Fused Phosphorus‐Nitrogen Heterocycles

控制吡啶-稠磷-氮杂环中的互变异构

• DOI: 10.1002/chem.202200472
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: McNeill, J. Nolan;Karas, Lucas J.;Bard, Jeremy P.;Fabrizio, Kevin;Zakharov, Lev N.;MacMillan, Samantha N.;Brozek, Carl K.;Wu, Judy I.;Johnson, Darren W.;Haley, Michael M.
• 通讯作者: Haley, Michael M.