Manipulation of the Interior and Exterior of Endohedral Fullerenes

这个奖项在无机，生物无机和有机化学计划支持教授艾伦L。为了研究内嵌富勒烯的外表面与其内部所含金属离子之间的相互作用，美国加州大学戴维斯分校的Balch博士进行了一项研究。X射线结构测定将在较大的内面体上进行，如M3N@C82和M3N@C84，其中理论预测违反孤立五边形规则（IPR）的结构应该受到青睐。 将使用克服许多困扰富勒烯晶体学的无序问题的共晶化技术。关于笼状碳原子的取向和化学相互作用，关于笼状碳原子的外部环境可以影响内部的金属离子的位置和特性。这些相互作用将通过检查还原对M3N@C80内面体结构的影响来系统地研究，以定义变化并揭示它们是否持久。将研究外部官能化对各种内面体的结构和化学行为的影响;特别是将检查氧化剂在内面体上的影响，因为内面体的氧化稳定性对于它们的最终用途是重要的，与有机金属试剂的反应将用于探测内嵌富勒烯中的反应位点，并探索内嵌富勒烯与空富勒烯之间化学行为的差异。笼状富勒烯影响结晶状态下内嵌富勒烯内金属离子取向的因素将在共结晶研究中进行研究，其中非内嵌和共结晶的性质将有所不同。本论文将探讨异质结构、笼状含金属离子的氮杂富勒烯结构的合成与结构。将测量具有顺磁性镧系离子的内嵌富勒烯在明确定义的结晶环境中的磁性。在电化学研究中，将检查通过电化学沉积内面体（特别是内部具有顺磁性镧系离子的那些内面体）和过渡金属络合物制成的氧化还原活性膜的电化学制备。内嵌富勒烯在生物医学应用中的应用正在积极研究中，包括用作MRI试剂和作为放射性药物的载体。 这项工作将有助于教育新一代的本科生，研究生和研究生在合成和结构化学，重点是内嵌富勒烯，但最终包括一系列的有机和无机化合物。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Alan L. Balch at the University of California at Davis to investigate the interplay between the outer surfaces of endohedral fullerenes and the metal ions contained inside. X-ray structure determinations will be performed on larger endohedrals such as M3N@C82 and M3N@C84 where theory predicts that structures violating the isolated pentagon rule (IPR) should be favored. Cocrystallization techniques that overcome many of the disorder problems that plague fullerene crystallography will be used. The external environment about the endohedral can affect the location and characteristics of the metal ions on the inside with regard to orientation and chemical interaction with the cage carbon atoms. These interactions will be systematically investigated by examining the effects of reduction on the structure of the M3N@C80 endohedrals in order to define the changes and uncover whether they are persistent. The effects of external functionalization on the structure and chemical behavior of various endohedrals will be studied; in particular, the effects of oxidants on endohedrals will be examined, since the oxidative stability of endohedrals is important to their eventual utility, reactions with organometallic reagents will be used to probe the reactive sites in endohedral fullerenes and explore differences in chemical behavior between the endohedral fullerenes and empty cage fullerenes. The factors influencing the orientation of the metal ions inside endohedral fullerenes in the crystalline state will be examined in cocrystallization studies where the nature of the non-endohedral and the cocrystallization will be varied. The synthesis and structures of hetero-endohedrals, endohedrals with azafullerene cages with metal ions inside will be examined. The magnetic properties of endohedral fullerenes with paramagnetic lanthanide ions in well-defined crystalline environments will be measured. The electrochemical preparation of redox-active films made by electrochemical deposition of endohedrals (particularly those with paramagnetic lanthanide ions inside) and transition metal complexes will be examined in electrochemical studies. Endohedral fullerenes are under active investigation for biomedical applications including use as MRI agents and as carriers of radiopharmaceuticals. This work will contribute the education of a new generation of undergraduate, graduate, and postgraduate students in synthetic and structural chemistry, with a focus on endohedral fullerenes but ultimately encompassing a range of organic and inorganic compounds.