Regioselective Addition of Perfluoroalkyl Radicals to Closed Carbon Surfaces

无机、生物无机和有机金属化学项目的这一奖项支持Steven H Strauss教授和Olga V. Boltalina教授的研究，他们的研究重点是基于富勒烯的一类新型氟化合物的合成、分离和表征。聚（全氟烷基）富勒烯（pafs）具有热稳定性（高达600℃）和化学稳定性，并产生相对稳定的自由基阴离子，可以作为结晶固体分离和研究。利用pi与C60、C70等富勒烯与RfI试剂的高收率、高温反应，制备出不同链长、组成和结构的系列pfa，用量为50-100+ mg。其他的合成方法将被探索，包括取代卤素原子在C60Xn和C70Xn衍生物。这些后一种反应可能产生动力学异构体，这将使一系列密切相关的富勒烯(X)n化合物的分子内异构化速率和机制首次得到详细研究。利用动态高效液相色谱监测技术优化反应条件以确定组分和同分异构体的纯度。PFAFs的刚性笼形结构，其中Rf基团与sp3 C原子相连，将提供一个独特的机会来推进对刚性sigma键系统中近似F原子之间的穿越空间费米接触耦合的理解。pafs的稳定性可能使其用于光电和纳米级电子器件，这将在与NREL的单独合作项目中进行探索。该项目涉及美国和海外的合作者，学生将与他们互动，这将扩大学生的教育，并帮助他们建立专业同事的网络。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professors Steven H Strauss and Olga V. Boltalina that focuses on the synthesis, isolation, and characterization of a new class of fluorochemical compounds based on fullerenes. Poly(perfluoroalkyl)fullerenes (PFAFs), are thermally (up to 600 C) and chemically stable and yield relatively stable radical anions, which may be isolated and studied as crystalline solids. Series of PFAFs, with varying chain lengths, compositions and structures will be prepared for the in 50-100+ mg quantities using the PIs' high-yield, high-temperature reactions of C60, C70, and other fullerenes with RfI reagents. Other synthetic methodologies will be explored, including substitution of halogen atoms in C60Xn and C70Xn derivatives. These latter reactions may produce kinetic isomers, which will allow the rates and mechanisms of intramolecular isomerization of a series of closely-related fullerene(X)n compounds to be studied in detail for the first time. Reaction conditions will be optimized for compositional and isomeric purity using a dynamic HPLC monitoring technique. The rigid cage structure of PFAFs, in which the Rf groups are attached to sp3 C atoms, will provide a unique opportunity to advance the understanding of through-space Fermi contact coupling between proximate F atoms in rigid sigma-bonded systems. The stability properties of PFAFs may allow them to be used for optoelectronic and nanoscale electronic devices, which would be explored in a separate collaborative project with NREL. The project involves collaborators in the US and abroad, with whom students will interact, which will broaden student education and help them build networks of professional colleagues.