Electron Transfer Photooxygenations With New and Improved Electron Transfer Sensitizers in Homogeneous and Heterogeneous Media

在均质和异质介质中使用新型和改进的电子转移敏化剂进行电子转移光氧合

• 批准号: 0646612
• 负责人: Edward Clennan
• 金额: --
• 依托单位: University of Wyoming
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-02-01 至 2011-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0646612&HistoricalAwards=false
• 关键词: Electron; Transfer; Photooxygenations; New; Improved

With this award, the Organic and Macromolecular Chemistry Program supports the work of Professor Edward L. Clennan of the University of Wyoming. This research will investigate the synthesis and characterization of a series of new light harvesting molecules that carry two positive charges for which the word pyrylogens has been suggested. The two positive charges have been incorporated in these new materials as a unique and key structural feature designed to provide superior performance as efficient photochemically initiated electron transfer (PET) catalysts. In contrast to other PET catalysts, electron transfer from a substrate to these pyrylogens will generate two repulsive positively charged species that will rapidly separate thereby preventing energy wasting back electron transfer. Preliminary studies have demonstrated that these molecules absorb light that closely mimics the solar spectrum and have superior optical properties that will allow excitation without competitive absorption by the substrates. Both their photochemical and electrochemical properties will be investigated. Further, the effectiveness of these new materials as electron transfer catalysts to introduce oxygen into organic molecules will be demonstrated. These new materials will also be imbedded in an inert matrix to generate stabilized heterogeneous catalysts that can be used in otherwise incompatible environments. Broader Impacts. Photochemically initiated electron transfer (PET) reactions are a broad fundamental class of transformations and as a consequence, the development of these new materials has far reaching impact well beyond the uses described in this proposal. Their use will represent a positive step toward the design of "greener" environmentally friendly processes that will allow access to new, otherwise inaccessible products. The heterogeneous catalysts derived from these materials have potential use as photocatalysts for the remediation of polluted wastewater since it is anticipated that they will function to degrade and mineralize organic pollutants. Finally, this project will provide an outstanding vehicle for the training of students who will enhance the scientific workforce.

有了这个奖项，有机和高分子化学计划支持教授爱德华L。怀俄明州大学的克莱南说。 本研究将研究一系列新的捕光分子的合成和表征，这些分子携带两个正电荷，因此建议使用pyryogens。 这两个正电荷已被纳入这些新材料作为一个独特的和关键的结构特征，旨在提供上级性能作为有效的光化学引发的电子转移（PET）催化剂。 与其他PET催化剂相比，从底物到这些吡喃基的电子转移将产生两种排斥性带正电荷的物质，其将快速分离，从而防止能量浪费的反向电子转移。 初步研究表明，这些分子吸收的光非常接近模拟太阳光谱，并具有上级光学性质，将允许激发，而不会被基板竞争性吸收。 它们的光化学和电化学性质将被研究。 此外，将证明这些新材料作为电子转移催化剂将氧引入有机分子的有效性。 这些新材料也将嵌入惰性基质中，以产生稳定的多相催化剂，可用于其他不相容的环境中。 更广泛的影响。光化学引发的电子转移（PET）反应是一种广泛的基本类型的转换，因此，这些新材料的开发具有远远超出本提案中所述用途的深远影响。 它们的使用将是朝着设计“更绿色”的环境友好工艺迈出的积极一步，这将使人们能够获得新的、否则无法获得的产品。 从这些材料衍生的非均相催化剂具有潜在的用途作为光催化剂用于污染废水的修复，因为它是预期的，它们将起到降解和矿化有机污染物。 最后，这个项目将提供一个优秀的工具，培养学生谁将提高科学劳动力。