开孔及氮杂内嵌金属富勒烯的合成研究

Several type of reactions of nitride clusterfullerenes and monometallofullerenes will be explored to synthesize open-cage endohedral fullerenes and azafullerenes, and thus manipulating their optical, electronic and magnetic properties. The reactions with aryl and alkyl azides are expected to afford open-cage monoadduct and bisadduct regioisomers of endohedral fullerenes. The reactions with bisazides connected with a spacer would result in open-cage endohedral fullerenes with two orifices. The reactions with benzynes in the presence of air will lead to metallofullerenes with a 13-membered-ring opening spanned by an oxygen atom and by a benzyne addend or other type of open-cage metallofullerenes. The reactions with tetrazines or analogs will give the corresponding open-cage metallofullerenes and further generate non-classical metallofullerenes with a 4-membered ring. The reactions with azide (CH3OCH2CH2O)CH2N3 will afford metallofullerenes with bisfulloid structures, which will be further transformed into metalloazafullerenes or their dimers.

将研究内嵌金属氮化物富勒烯、内嵌单金属富勒烯的若干反应，合成开孔内嵌金属富勒烯与内嵌金属氮杂富勒烯，从而调控内嵌金属富勒烯的光电磁性能。与芳基叠氮化合物、烷基叠氮化合物反应，合成内嵌金属富勒烯的单加成及双加成开孔产物区域异构体；与含一个桥连“筑块”的双叠氮化合物反应，区域选择地合成多种双开孔内嵌金属富勒烯；与原位生成的苯炔在空气中反应，试图得到四元环及氧化产生的环氧同时开环的13元环或其它类型开孔内嵌金属富勒烯；与四嗪或类似物的反应，试图得到相应开孔内嵌金属富勒烯以及含四元环的非经典内嵌金属富勒烯；与叠氮化物(CH3OCH2CH2O)CH2N3反应，得到相应的双氮杂开孔内嵌金属富勒烯，然后再转化为内嵌金属氮杂富勒烯或其二聚体。

富勒烯及其衍生物在材料科学、生物医药等具有广泛的应用前景。本项目围绕富勒烯新反应及开孔富勒烯化合物的合成，开展了内嵌金属富勒烯Sc3N@C80、Y3N@C80等在氧气存在下与取代芳基叠氮的芳基开环反应意外选择性地生成双烯取代的异噁唑并内嵌金属富勒烯衍生物；内嵌金属富勒烯Sc3N@C80与叠氮化合物反应生成氮杂桥双加成内嵌金属富勒烯衍生物；内嵌金属富勒烯Sc3N@C80与苯炔在氧气氛下反应选择性生成单一的内嵌金属富勒烯的环氧开环的双加成产物；内嵌金属富勒烯Sc3N@C80与3,6-二(2-吡啶基)-1,2,4,5-四嗪反应意外生成了吡唑啉并内嵌金属富勒烯产物；内嵌金属富勒烯Sc3N@C80与亚硝酸异戊酯在氩气保护下光照反应生成了罕见的内嵌金属富勒烯并氧杂七元环产物和内嵌金属富勒醇产物；研究了内嵌金属富勒烯Sc3N@C80与溴代丙二酸乙酯或二芳基重氮化合物等的双加成反应；同时还开展了富勒烯化合物的合成方法学研究。