RUI - Ferrocene - containing panchromatic BODIPY, azaBODIPY, and porphyrin nanocarbon assemblies for light-harvesting

在这个项目中，明尼苏达大学德卢斯分校化学系的Viktor Nemykin教授将在化学系化学结构、动力学和机理B项目的资助下，开发新型的含二茂铁的纳米碳硼-二吡啶（BODIPY）、azaBODIPY和卟啉超分子组装体。本研究的目标是利用这些供体-受体超分子超结构的特性，将太阳能光能转化为存储的化学能或电能（例如有机光伏电池）。该项目位于有机、有机金属、无机、材料和理论化学的界面，因此非常适合本科生和研究生（M.S.）科学家的教育。它还将为本科生提供优秀的教育和实践实验培训，包括在科学领域代表性不足的群体的成员。本提案的重点是设计和表征新的全色BODIPYs， azaBODIPYs和连接到氧化还原活性供体（二茂铁）和受体（富勒烯，碳纳米管，石墨烯）中心的卟啉。所提出的富勒烯/纳米管/石墨烯的超分子组件可能对光收集有用。在提出的研究中，BODIPYs， azaBODIPYs和卟啉将被用作本质上是平面的，高度共轭的平台，这有助于在氧化还原活性中心之间进行远距离金属-金属耦合和有效的电子转移。在计划的工作中，有机金属氧化活性中心将与BODIPY、azaBODIPY或卟啉核心共价连接，以制备具有几何和电子结构系统性变化的各种系统。这些供体天线二联体将进一步与纳米碳衍生物如富勒烯、碳纳米管或石墨烯共价或非共价连接。对所提出的化合物的系统研究将有助于了解pi共轭平台的性质、氧化还原中心之间的通键和通空间距离以及与天线pi系统的供体和受体共轭的类型如何以及在多大程度上控制这些系统中的氧化还原过程、稳定性和光致电子转移性质。长期目标包括对复杂氧化还原活性卟啉型超分子阵列的结构、反应性和电子相互作用的基本知识的基本理解和改进，寻找对分子电子学、光捕获、催化和光催化应用有用的芳香pi系统，以及创造新的方法来制备具有有用性质的卟啉及其类似物。

In this project, Professor Viktor Nemykin of the Department of Chemistry at University of Minnesota Duluth, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, will develop new classes of ferrocenyl-containing nanocarbon boron-dipyrromethene (BODIPY), azaBODIPY, and porphyrin supramolecular assemblies. The goal of this research is to exploit the characteristics of these donor-acceptor supramolecular superstructures for systems for solar light energy conversion into stored chemical energy or electricity (e.g. organic photovoltaic cells). The project lies at the interface of organic, organometallic, inorganic, materials, and theoretical chemistry, and is thus well designed for the education of undergraduate and graduate (M.S.) scientists. It will also provide excellent education and hands-on experimental training for undergraduate students including members of groups underrepresented in science. This proposal centers on the design and characterization of new panchromatic BODIPYs, azaBODIPYs, and porphyrins connected to redox-active donor (ferrocene) and acceptor (fullerene, carbon nanotube, graphene) centers. The proposed supramolecular assemblies with fullerenes/nanotubes/graphene might be useful for light-harvesting. In the proposed research, BODIPYs, azaBODIPYs, and porphyrins will be used as essentially planar, highly conjugated platforms, which is useful for a long-range metal-metal coupling and effective electron-transfer between redox-active centers. In the planned work, organometallic redox-active centers will be covalently linked to BODIPY, azaBODIPY, or porphyrin core in order to prepare a variety of systems with systematic variation in geometric and electronic structures. These donor-antennae dyads will be further covalently or non-covalently linked to the nanocarbon derivatives such as fullerenes, carbon nanotubes, or graphene. The systematic investigation of proposed compounds will help to understand how and to what extent the nature of the pi-conjugated platform, the through-bond and through-space distance(s) between the redox centers, and the type of donor and acceptor conjugation with the antennae pi-system can control redox processes, stability, and photo-induced electron-transfer properties in these systems. The long-term goals include the fundamental understanding and improvement of a basic knowledge on structure, reactivity, and electronic interactions in complex redox-active porphyrinoid-type supramolecular arrays, the search for aromatic pi-systems useful for applications in molecular electronics, light-harvesting, catalysis, and photocatalysis, and the creation of new methodologies for preparation of porphyrins and their analogues with useful properties.