CAREER: Boracycles with Unusual Bonding as Creative Strategies for Main-Group Functional Materials

在化学系化学合成项目的支持下，弗吉尼亚大学化学系的Robert Gilliard博士正在研究硼掺杂有机分子的合成，以推进有机发光二极管（OLED）材料的发展。含有碳氮环的化合物在新药开发和其他医学应用中具有多种应用。然而，当这些环状化合物中的选定碳原子被硼取代时，就会产生特殊的性质，使这些“硼掺杂”分子发光和/或变色，使它们适合于电视、手机和电脑显示器等电子产品的进步。仍然存在的挑战是开发低成本和持久的材料，吸收或发射特定颜色和强度的光。这可以通过将硼与非金属元素（如磷）或金属（如金）偶联来实现。该项目还包括旨在提高代表性不足的少数民族和弗吉尼亚社区学院学生的教育成功率和毕业率的外展活动，这些学生转到弗吉尼亚大学完成学士学位。这些学生将有机会进行科学、技术、工程和数学（STEM）研究，并将获得特定学位的指导和专业发展，为研究生院和科学事业做好准备。该项目的目标是开发新的合成方法，并建立具有异常键合的低价硼环材料的反应性趋势。今后将重点研究稳定的开壳硼自由基的合成，用于能量的储存和转化。主要的合成策略将包括化学还原合适的卤代环起始材料。这些自由基的氧化还原和电子性质将通过实验和理论研究，以获得不寻常的自旋态，用于光电材料的设计。该项目的另一个目标是研究硼杂原子掺杂材料的合成和光物理性质。这将涉及两种主要策略：a)磷烯从硼磷烯烯材料转移并随后进行环扩张以形成6和8元硼磷掺杂杂环；b)使用新型硼环阴离子亲核取代以形成硼过渡金属和硼主基团元素材料。来自弗吉尼亚当地社区学院的转学生和未被充分代表的少数族裔本科生将参与这些研究活动，旨在提供高质量的教育和技术培训，从而增加STEM劳动力的多样性。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis Program of the Division of Chemistry, Dr. Robert Gilliard of the University of Virginia, Department of Chemistry, is studying the synthesis of boron doped organic molecules to advance of organic light emitting diode (OLED) materials. Compounds containing carbon-nitrogen rings have a variety of applications in the development of new drugs and other medical applications. However, when select carbon atoms are replaced with boron in these cyclic compounds, special properties are induced that cause these “boron-doped” molecules to emit light and/or change color, making them suitable for the advancement of electronics such as television, cell phone, and computer displays. A challenge that remains is the development of low-cost and long-lasting materials that absorb or emit light with specific colors and intensity. This can be achieved by coupling boron with non-metal elements such as phosphorus, or metals like gold. This project also contains outreach activities aimed at increasing educational success and graduation rates for underrepresented minorities and Virginia community college students who transfer to the University of Virginia to complete a bachelor’s degree. These students will have the opportunity to conduct science, technology, engineering, and mathematics (STEM) research and will receive degree-specific mentoring and professional development, enhancing their preparedness for graduate school and careers in science.The goals of the project are to develop new synthetic methods and establish reactivity trends for low-valent boracyclic materials with unusual bonding. Significant effort will be focused on the synthesis of stable open-shell boron radicals for energy storage and conversion. The primary synthetic strategy will involve chemical reduction of suitable haloboracyclic starting materials. The redox and electronic properties of these radicals will be studied with experiment and theory to access unusual spin states for the design of optoelectronic materials. An additional goal of the project is to investigate the synthesis and photophysical properties of boron-heteroatom-doped materials. This will involve two primary strategies: a) phosphinidene transfer from boraphosphaketene materials and subsequent ring expansion to form 6- and 8-membered boron-phosphorus-doped heterocycles and b) nucleophilic substitution using novel boracyclic anions to form boron-transition metal and boron-main-group element materials. Transfer students from local Virginia community colleges and underrepresented minority undergraduates will participate in these research activities, with the aim of providing high-quality educational and technical training, thereby increasing the diversity of the STEM workforce.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.