Pyrroles, (aza)Dipyrrins and their Complexes: Synthesis and Properties

吡咯、(氮杂)二吡啶及其配合物：合成与性质

• 批准号: RGPIN-2021-02989
• 负责人: Thompson, Alison
• 金额: $ 2.62万
• 依托单位: Dalhousie University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748126
• 关键词: Pyrroles; aza; Dipyrrins; their; Complexes

Modern synthetic chemistry involves the design and preparation of molecular constructs with properties that match, or are predicted to match, desired functions such as catalytic activity, bioactivity, optical properties, electrochemical performance, solubility and reactivity. Trainees contributing to the Thompson Discovery Grant research program at Dalhousie University will devise synthetic methodologies for (oligo)pyrrole preparation and functionalization, generating frameworks with rich (photo)physical properties. This research involves harnessing the five-membered nitrogen-containing aromatic pyrrolic unit, a motif used to spectacular effect by nature (e.g. in heme and chlorophyll) yet extremely challenging for chemists to manipulate courtesy of its electron-rich core and notoriously high reactivity. This research provides training in synthetic chemistry, plus the determination and application of properties exhibited by chemical species. Trainees will develop competencies in synthetic sequence design, anhydrous reaction techniques, purification strategies and a broad range of compound characterization methods. These competencies are key to the growing bio-sector and energy-related industries in Canada. The ability to predict and apply structure-function relationships is critical to the invention and development of materials and matter used in devices, agriculture and the pharmaceutical industry. In addition to technical competences, the training environment provides opportunities to enhance skills such as effective communication and collaboration to enhance readiness for the career workplace. The goals of this research program are embraced through four objectives, interconnected through the necessity to develop routes by which to synthesize and functionalize pyrroles in a controlled and desired manner: 1.The design and development of routes to first-in-class tellurium-substituted BODIPYs (4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes) will enable these molecular constructs to be evaluated as (complementary) photosensitizers and mass cytometry labels for use in biosensing. This research will involve the development of new and robust methodology for the synthesis and cross-coupling of tellurophenes, an achievement that will have impact far beyond pyrrole-based chemistry. 2.Synthetic methods towards aza-BODIPYs, stable dipyrrolic constructs that absorb/emit into the (far) red, will be investigated so that chiral motifs can be reliably incorporated: these molecular constructs have promise in dual-channel sensing. 3.Novel (bis)pyrrolic and bis(ruthenium)-pyrrolide triad frameworks featuring p-expansive (pi-expansive) linkers will be explored for their materials and photosensitizing properties. 4.Synthetic methods towards dipyrrolic azo-compounds will be determined, thereby providing a tunable new chemical class for use in photochemical switching and sensing.

现代合成化学涉及设计和制备分子结构，其性质符合或预计符合所需的功能，如催化活性、生物活性、光学性质、电化学性能、溶解度和反应性。为达尔豪斯大学汤普森发现基金研究项目做出贡献的学员将设计（寡）吡咯制备和功能化的合成方法，生成具有丰富物理性质的框架（照片）。这项研究涉及到利用五元含氮的芳香吡啶单元，这种基序在自然界中（例如在血红素和叶绿素中）具有惊人的效果，但由于其富含电子的核心和出了名的高反应性，对化学家来说极具挑战性。这项研究提供了合成化学方面的训练，以及化学物质所表现出的性质的测定和应用。学员将在合成序列设计、无水反应技术、纯化策略和广泛的化合物表征方法方面发展能力。这些能力是加拿大不断发展的生物部门和能源相关行业的关键。预测和应用结构-功能关系的能力对于设备、农业和制药工业中使用的材料和物质的发明和发展至关重要。除了技术能力之外，培训环境还提供了提高技能的机会，例如有效的沟通和协作，以提高对职业工作场所的准备。本研究计划的目标包括四个目标，通过开发以可控和理想的方式合成和功能化吡咯的途径的必要性，这些目标相互联系：设计和开发一流的碲取代BODIPYs（4,4-二氟-4-硼-3a，4 -二氮-s-吲哚烯）的路线将使这些分子结构能够被评估为（互补）光敏剂和用于生物传感的大量细胞计数标记。这项研究将涉及开发新的和强大的方法来合成和交叉偶联碲苯，这一成就的影响将远远超出基于吡咯的化学。2.aza-BODIPYs是一种稳定的双吡咯结构体，可以吸收/发射到（远）红色，将研究其合成方法，以便可以可靠地结合手性基序：这些分子结构体在双通道传感中具有前景。3.新型（双）吡咯烷和双（钌）吡咯烷三元框架具有p-膨胀（pi-膨胀）连接将探索其材料和光敏性能。4.将确定二吡咯偶氮化合物的合成方法，从而为光化学开关和传感提供可调的新化学类别。