Manipulation of the Interior and Exterior of Endohedral Fullerenes

这个无机、生物无机和有机金属化学项目的奖项支持加州大学戴维斯分校的Alan L. Balch教授研究内嵌富勒烯的外表面和里面的金属离子之间的相互作用。x射线结构测定将在较大的内腔上进行，如M3N@C82和M3N@C84，理论预测违反孤立五边形规则（IPR）的结构应该更有利。共结晶技术克服了许多困扰富勒烯晶体学的无序问题。内嵌体的外部环境会影响金属离子在内嵌体内部的位置和特性，包括取向和与笼状碳原子的化学相互作用。这些相互作用将通过检查还原对M3N@C80内壁结构的影响来系统地研究，以确定变化并揭示它们是否持久。研究了外功能化对各种内源性化合物的结构和化学行为的影响；特别是，氧化剂对内嵌体的影响将被检查，因为内嵌体的氧化稳定性对它们的最终用途很重要，与有机金属试剂的反应将被用来探测内嵌体富勒烯的活性位点，并探索内嵌体富勒烯和空笼富勒烯之间的化学行为差异。在共结晶研究中，将研究影响内嵌富勒烯中金属离子取向的因素，其中非内嵌富勒烯和共结晶的性质将有所不同。研究了异质内嵌体、氮杂烯笼内嵌体的合成和结构。将测量具有顺磁性镧系离子的内嵌富勒烯在明确的晶体环境中的磁性。在电化学研究中，将研究通过电化学沉积内嵌体（特别是内部有顺磁性镧系离子的内嵌体）和过渡金属配合物制备氧化还原活性薄膜的电化学方法。内嵌富勒烯正在积极研究其在生物医学上的应用，包括作为核磁共振试剂和放射性药物的载体。这项工作将有助于新一代的本科生、研究生和研究生在合成和结构化学方面的教育，重点是内嵌富勒烯，但最终包括一系列有机和无机化合物。

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.