Oligopyrrole Macrocycles: Synthesis, Electronic Structure, Switching, and Communication

低聚吡咯大环化合物：合成、电子结构、开关和通信

• 批准号: 1807152
• 负责人: Jonathan Sessler
• 金额: $ 68万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2020-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1807152&HistoricalAwards=false
• 关键词: Oligopyrrole; Macrocycles; Synthesis; Electronic; Structure

Professor Jonathan L. Sessler and his team at The University of Texas at Austin supported by this award are exploring new analogues of the pigments that make blood red, vitamin B12 purple, and grass green. Also targeted for study are the principles of chemical communication that biology uses to transmit signals over short distances and long as exemplified, for instance, by neuroregulators and skunk sprays, respectively. By using small molecules to trigger downstream chemical events it could become possible to probe the complexity of biology within the chemical laboratory. With such long-term goals in mind, new molecules have been designed that are expected to advance our understanding of how molecular structure affects key properties, such as color, stability, and an ability to interact with other chemical entities. This is expected, in term, to lead to the development of new molecular systems that can be used to create information storage arrays or being used in the context of new medical modalities, such as photodynamic therapy, where light is used to treat diseases. This project involves work that spans the gamut of chemistry sub-areas. It is thus expected to enhance coworker training and provide a technically savvy workforce. It also should also provide an opportunity for young researchers to develop the skills needed to pursue academic or non-academic research-related careers.In terms of specifics, this project focuses on two classes of oligopyrrole macrocycles that have benefited from prior NSF support, namely expanded porphyrins and calixpyrroles. These molecules, alone and in concert, are being used to pursue the following specific aims, which involve respectively: 1) The preparation of new two- and three-dimensional expanded porphyrins. These systems allow explorations of the effects of oxidation, reduction, and donor-acceptor interactions on both ground and excited state (anti)aromaticity. They also allow determinations of which design features control localized vs. delocalized aromaticity and radical vs. closed shell conjugation pathways and thus advances in basic structure-function understanding as it relates to blood pigment analogues; 2) the synthesis of functionalized calixpyrrole systems that can access multiple discrete states, such as helices, capsules, and discrete monomers. In the context of this aim, off-equilibrium effects are being explored using chiral, non-racemic pyridine-functionalized calixpyrroles and their interactions with metalated expanded porphyrins; 3) further explorations of a previously reported benzotetrathiafulvalene calixpyrrole-TCNQ ensemble, particularly in the context of its ability to release ionic and molecular messengers and mediate various downstream chemical reactions. Combinations of monomeric and capsule-type calixpyrroles with expanded porphyrins, are being explored with a view to creating more complex information transfer systems. In this way, the effect of structure on cascade-like signal transduction in completely synthetic constructs can be assessed. Ultimately, this could lead to systems capable of highly dense information storage or able to perform rudimentary computing functions. This project is expected to be accomplished in four years.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.

乔纳森·l·塞斯勒教授和他在德克萨斯大学奥斯汀分校的团队得到了该奖项的支持，他们正在探索使血液变红、维生素B12变紫和草变绿的色素的新类似物。研究的另一个目标是化学通讯的原理，生物学用它来传递短距离和长距离的信号，例如，神经调节剂和臭鼬喷雾。通过使用小分子来触发下游的化学事件，在化学实验室里探测生物的复杂性成为可能。考虑到这样的长期目标，新分子的设计有望促进我们对分子结构如何影响关键特性的理解，如颜色、稳定性和与其他化学实体相互作用的能力。预计这将导致新的分子系统的发展，这些系统可用于创建信息存储阵列或用于新的医学模式，例如光动力疗法，其中用光来治疗疾病。这个项目涉及的工作跨越了化学子领域的范围。因此，它有望加强同事培训，并提供一支精通技术的劳动力队伍。它还应该为年轻研究人员提供机会，发展从事学术或非学术研究相关职业所需的技能。具体而言，本项目侧重于两类受益于NSF先前支持的低聚吡咯大环，即扩展卟啉和杯吡咯。这些分子，单独或协同，正被用于追求以下具体目标，分别涉及：1)制备新的二维和三维扩展卟啉。这些系统允许探索氧化，还原和供体-受体相互作用对基态和激发态（抗）芳香性的影响。它们还允许确定哪些设计特征控制局部与非局部芳香性以及自由基与封闭壳偶联途径，从而在与血液色素类似物相关的基本结构-功能理解方面取得进展；2)可以进入多个离散态的功能化杯吡咯体系的合成，如螺旋、胶囊和离散单体。在此背景下，利用手性、非外消旋吡啶功能化的杯吡咯及其与金属化扩展卟啉的相互作用，研究了非平衡效应；3)进一步探索先前报道的苯并四噻吩环吡咯- tcnq系综，特别是在其释放离子和分子信使并介导各种下游化学反应的能力的背景下。目前正在探索单体和胶囊型杯吡咯与扩展卟啉的组合，以创建更复杂的信息传递系统。通过这种方式，可以评估结构对完全合成结构中级联样信号转导的影响。最终，这可能导致系统能够高度密集的信息存储或能够执行基本的计算功能。这个项目预计在四年内完成。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Regulating the Structures of Self-Assembled Mechanically Interlocked Moleculecular Constructs via Dianion Precursor Substituent Effects

• DOI: 10.1021/jacs.9b13473
• 发表时间: 2020-04-22
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Chen, Xu-Lang;Shen, Yun-Jia;Gong, Han-Yuan
• 通讯作者: Gong, Han-Yuan

Semiconducting Supramolecular Organic Frameworks Assembled from a Near-Infrared Fluorescent Macrocyclic Probe and Fullerenes

• DOI: 10.1021/jacs.0c03699
• 发表时间: 2020-07-01
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Kaur, Ramandeep;Sen, Sajal;Jana, Atanu
• 通讯作者: Jana, Atanu

Synthesis of α,α’-linked penta- and septaheterocycles by tandem Suzuki coupling

通过串联 Suzuki 偶联合成 α,α-连接的五杂环和七杂环

• DOI: 10.1142/s1088424618501080
• 发表时间: 2019
• 期刊: Journal of Porphyrins and Phthalocyanines
• 影响因子: 1.5
• 作者: Zafar, Hadiqa;Brewster, James T.;Wight, Christopher D.;McVeigh, Matthew;Steinbrück, Axel;Lynch, Vincent M.;Sessler, Jonathan L.
• 通讯作者: Sessler, Jonathan L.

Expanding the Porphycene Core: Modification and Metalation

• DOI: 10.1055/s-0037-1610345
• 发表时间: 2018-12
• 期刊: Synlett
• 影响因子: 2
• 作者: James T. Brewster;Gonzalo Anguera;J. Sessler

Three-Dimensional Fully Conjugated Carbaporphyrin Cage

• DOI: 10.1021/jacs.8b11158
• 发表时间: 2018-12-05
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ke, Xian-Sheng;Kim, Taeyeon;Sessler, Jonathan L.
• 通讯作者: Sessler, Jonathan L.