CAS: Prodigious 2- and 3-Dimensional Organic Electron Acceptors via Strategic Cyclizations with Perfluoro Substituents

在化学系化学结构、动力学和机理B(CSDM-B)计划的支持下，科罗拉多州立大学的Olga Boltalina博士正在研究有效的方法来控制(多)氟碳环与多环芳烃(PAHs)的加成，以扩大它们的共轭体系，这可能会导致电荷传输、热稳定性和抗光氧化性能的关键增强，从而延长器件寿命；在给体-受体共混物中光致电荷产生的良好的形貌和电子性质。该项目预计将影响电子以外的材料设计：液晶、农用化学品、光子学、手性材料、自旋电子学、含氟化合物的医学成像(F-MRI、PET)和制药。其他更广泛的社会效益包括该项目对高性能有机接受器潜在变革性技术进步的贡献，这些有机接受器具有优异的空气、湿度、光和热稳定性，将被集成到低成本、高效、可持续和耐用的设备中，包括有机场效应晶体管、有机发光设备和可以与建筑或车辆集成的太阳能电池，从而明显增加可再生能源在日常生活中的使用并降低成本。博尔塔里纳博士的目标是将尖端研究与教育和专业发展计划结合起来，面向研究生和暑期研究少数群体(以及其他代表性不足的群体)化学专业的学生，让他们参与国家和国际合作，并为他们提供从学术界到行业成功职业所需的技能。该项目将部署一系列氟化学方法来设计、合成和测试新型n型有机氟半导体的电荷迁移率。商业上可用的多环芳烃和全氟烷基(苄基)碘将用于一锅反应，以促进全氟碳环的加成和随后的还原脱氟，从而在多环芳烃上生成芳香族或非芳族六元、五元甚至七元氟化环。对这些新转化的系统实验和计算研究有望增进对化学反应途径的基本理解，有助于优化反应选择性和整体效率。电荷输运数据将被用来确定氟碳环在促进高度有序的有机氟半导体的电荷迁移率方面的具体作用。电子亲和力的增加和更大的固态有序性对这些材料作为n型半导体、p掺杂和自组装单分子膜的功能增强的影响将被探索。新类型的(多)氟化多环芳烃构建块以前无法通过其他方法获得，但很可能为更广泛的合成社区提供，用于在共价有机框架、生物传感、荧光染料和电子材料中使用氟化学。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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 Structure, Dynamics, and Mechanisms B (CSDM-B) Program in the Division of Chemistry, Dr. Olga Boltalina of Colorado State University is studying efficient methods for controlled addition of (poly)fluorinated carbacycles to polycyclic aromatic hydrocarbons (PAHs) to expand their conjugated systems, which may result in the critical enhancement of charge transport, thermal stability, resistance to photooxidation, and hence, longer device lifetimes; favorable morphology and electronic properties for photoinduced charge generation in donor-acceptor blends. The project is anticipated to impact material design beyond electronics: liquid crystals, agrochemicals, photonics, chiroptical materials, spintronics, medical imaging with fluorinated compounds (F-MRI, PET) and pharmaceuticals. Other broader societal benefits include the project's contribution to potentially transformational technological advances in high-performing organic acceptors with superior air-, moisture-, light-, and thermal stability that will be integrated into low-cost, efficient, sustainable, and durable devices, including organic field effect transistors, organic light-emitting devices and solar cells that can be building- or vehicle-integrated, thereby visibly increasing the use and lowering costs of renewable energy sources in everyday life. Dr. Boltalina aims to combine cutting-edge research with educational and professional development program for postgraduate students and summer research minority- and other underrepresented-group chemistry majors by involving them in national and international collaborative work and providing them with the skill sets that they need for successful careers from academia to industry.The project will deploy an arsenal of fluorine chemistry methods to design, synthesize and test the charge mobility of new n-type organofluorine semiconductors. Commercially available PAHs and perfluoroalkyl (benzyl) iodides will be used in one-pot reactions to promote the addition of perfluorinated carbacycles and subsequent reductive defluorination leading to aromatic or non-aromatic six-, five- or even seven-membered fluorinated rings on PAHs. Systematic experimental and computational studies of these new transformations are expected to improve fundamental understanding of chemical reaction pathways, to help optimize reaction selectivity and overall efficiency. Charge transport data will be used to determine the specific roles of fluorocarbacycles in the facilitation of charge mobility of highly ordered organofluorine semiconductors. The effects of increased electron affinity and greater solid-state ordering on functional enhancements of these materials as n-type semiconductors, p-dopants, and self-assembled monolayers will be explored. New types of (poly)fluorinated PAH building blocks that had been inaccessible by other methods may well become readily available to the broader synthetic community for the utilization of fluorine chemistry in covalent organic frameworks, biosensing, fluorescent dyes, and electronic materials.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.