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

RUI - 二茂铁 - 含有全色 BODIPY、azaBODIPY 和卟啉纳米碳组件，用于光捕获

• 批准号: 1464711
• 负责人: Paul Kiprof
• 金额: $ 33万
• 依托单位: University of Minnesota Duluth
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464711&HistoricalAwards=false
• 关键词: RUI; Ferrocene; containing; panchromatic; BODIPY

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.

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、动态和机理B计划的资助下，开发新型的含二茂铁基纳米碳硼-二吡咯亚甲基(BODIPY)、氮杂BODIPY和卟啉超分子组装体。这项研究的目的是利用这些施主-受体超分子超结构的特点，将太阳能转化为储存的化学能或电能的系统(例如有机光伏电池)。该项目位于有机、有机金属、无机、材料和理论化学的交界处，因此适合本科生和研究生的教育。科学家们。它还将为本科生提供极好的教育和动手实验培训，包括在科学领域代表性不足的群体成员。这项建议的核心是设计和表征新的全色BODIPY、氮杂BODIPY和连接到氧化还原活性的给体(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/石墨烯超分子组装体可能对捕光有用。在拟议的研究中，BODIPY、氮杂BODIPY和卟啉将被用作基本平面的、高度共轭的平台，这对于远程金属-金属耦合和氧化还原活性中心之间的有效电子转移是有用的。在计划的工作中，有机金属氧化还原活性中心将共价连接到BODIPY、azaBODIPY或卟啉核心，以制备各种几何结构和电子结构具有系统变化的体系。这些施主-天线二元体将进一步共价或非共价连接到纳米碳衍生物，如富勒烯、碳纳米管或石墨烯。对所提出的化合物的系统研究将有助于理解pi共轭平台的性质、氧化还原中心之间的穿透键和穿透空间距离(S)以及与天线pi体系的给体和受体共轭的类型如何以及在多大程度上控制这些体系中的氧化还原过程、稳定性和光诱导电子转移性质。长期目标包括对复杂氧化还原活性的卟啉类超分子阵列的结构、反应性和电子相互作用的基本知识的基本了解和提高，寻找可用于分子电子学、光捕获、催化和光催化的芳香族PI体系，以及创建制备具有有用性质的卟啉及其类似物的新方法。