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

现代合成化学涉及分子构建体的设计和制备，所述分子构建体具有匹配或预测匹配所需功能的性质，例如催化活性、生物活性、光学性质、电化学性能、溶解度和反应性。为达尔豪西大学的汤普森发现资助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（照片）物理特性的框架。这项研究涉及利用五元含氮芳香族吡咯单元，这是一种自然界中用于产生壮观效果的基序（例如血红素和叶绿素），但由于其富含电子的核心和众所周知的高反应性，化学家操纵起来极具挑战性。这项研究提供了合成化学方面的培训，以及化学物种所表现出的特性的确定和应用。学员将发展合成序列设计，无水反应技术，纯化策略和广泛的化合物表征方法的能力。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开发至关重要。除了技术能力，培训环境提供了机会，以提高技能，如有效的沟通和协作，以提高准备工作的职业生涯。该研究计划的目标通过四个目标来实现，这些目标通过开发以受控和期望的方式合成和官能化吡咯的路线的必要性相互关联：1.一流的碲替代BODIPY路线的设计和开发（4，4-二氟-4-硼杂-3a，4 α-二氮杂-S-引达省）将使得这些分子构建体能够被评估为用于生物传感的（互补）光敏剂和质谱细胞计数标记。这项研究将涉及开发新的和强大的方法，用于合成和交叉偶联碲吩，这一成就的影响将远远超出基于吡咯的化学。2.氮杂-BODIPY的合成方法，稳定的二吡咯结构，吸收/发射到（远）红色，将进行研究，使手性基序可以可靠地纳入：这些分子结构有希望在双通道传感。3.新型的（双）吡咯和双（钌）-吡咯三单元框架具有p-膨胀（pi-膨胀）连接器将探索其材料和光敏性能。4.对二吡咯偶氮化合物的合成方法将被确定，从而提供一个可调的新的化学类别用于光化学开关和传感。

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.