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.

现代合成化学涉及分子结构的设计和制备，其性能匹配或预计匹配所需的功能，如催化活性、生物活性、光学性能、电化学性能、溶解度和反应性。为达尔豪斯大学汤普森发现资助研究项目做出贡献的学员将设计用于（低聚）吡咯制备和功能化的合成方法，生成具有丰富（照片）物理特性的框架。这项研究涉及利用五元含氮芳香吡咯单元，该基序在自然界中具有惊人的效果（例如在血红素和叶绿素中），但由于其富含电子的核心和众所周知的高反应性，对化学家来说操纵起来极具挑战性。这项研究提供合成化学方面的培训，以及化学物质所表现出的特性的测定和应用。学员将培养合成序列设计、无水反应技术、纯化策略和广泛的化合物表征方法方面的能力。这些能力对于加拿大不断发展的生物行业和能源相关行业至关重要。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开发至关重要。除了技术能力之外，培训环境还提供了增强有效沟通和协作等技能的机会，以增强为职业工作场所做好准备。该研究计划的目标包括四个目标，这些目标通过开发以受控和期望的方式合成和功能化吡咯的路线的必要性而相互关联： 1. 设计和开发一流的碲替代路线BODIPY（4,4-二氟-4-bora-3a,4a-二氮杂-s-indacenes）将使这些分子结构能够作为（补充）光敏剂和质量进行评估用于生物传感的细胞计数标记。这项研究将涉及开发新的、稳健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.将研究aza-BODIPY（吸收/发射到（远）红色光的稳定二吡咯结构）的合成方法，以便可靠地掺入手性基序：这些分子结构在双通道传感中具有前景。 3.将探索具有p-膨胀（pi-膨胀）连接基的新型（双）吡咯和双（钌）-吡咯化物三联体框架的材料和光敏特性。 4.将确定二吡咯偶氮化合物的合成方法，从而提供用于光化学开关和传感的可调节的新化学类别。