内嵌金属钇富勒烯的制备、分离与结构
摘要
内嵌金属富勒烯的物理化学性质，分子电子性质，几何结构等与空心富勒烯有很大不同。由于其结构新奇美观、性质奇特，内嵌金属富勒烯在光学、磁学、分子电子器件及生物医学工程等诸多高科技领域有广阔的应用前景。然而由于内嵌金属富勒烯产率低、种类多、分离困难等而限制了广泛深入的研究。
本论文首先，采用传统的电弧放电法对钇源进行选择；其次，使用四种烟炱前处理方法对提取方法进行选择；再次，通过柱色谱富集实验富集大量内嵌金属富勒烯样品，进一步缩短内嵌金属钇富勒烯的分离时间，提高分离效率；最后通过多步高效液相色谱分离、MS、Vis-NIR、CV和13CNMR检测，得到纯度很高（>95%）的多种内嵌金属钇富勒烯：Y2C82（Ⅰ、Ⅲ），Y2C84（Ⅰ、Ⅲ），Y2C90（Ⅰ），Y2C92（Ⅰ、Ⅱ）和Y@C82，并确定Y2C2@C82（Ⅲ）和Y2@C82（Ⅲ）的分子结构同属C82-C3v（8）。
Endohedral Metallofullerenes (EMFs) which are different from fullerenes in various properties such as chemical and physical properties, molecule and electrical properties, electronic structures, have a wide range of potential applications in photoelectrochemical materials, magnetic resonance imaging contrast agents, and medical diagnosis. Because of the low yields, various species (e.g., various metals, cage sizes, and symmetries) and difficult purification, these attractive molecules are also not widely or deeply researched.
In this paper, we prepare the soot by classic DC arc discharge with various sources of yttrium, isolate the soot by means of four diverse treatments, and with the help of column chromatographic isolation, we enrich a great quantity of yttrium metallofullerenes. Finally, a series of Y metallofullerenes based on different fullerene cages, i.e. Y2C80(I), Y2C82(I, III), Y2C84(I, III), Y2C90(I), Y2C92(I, II) and Y@C82are successfully isolated by multi-steps HPLC, and we also confirm that the structure of Y2@C82(IIII) is exactly the same as that of Y2C2@C82(III), i.e. C82-C3v (8), detected by MS, Vis-NIR, CV,13C NMR.
本论文首先，采用传统的电弧放电法对钇源进行选择；其次，使用四种烟炱前处理方法对提取方法进行选择；再次，通过柱色谱富集实验富集大量内嵌金属富勒烯样品，进一步缩短内嵌金属钇富勒烯的分离时间，提高分离效率；最后通过多步高效液相色谱分离、MS、Vis-NIR、CV和13CNMR检测，得到纯度很高（>95%）的多种内嵌金属钇富勒烯：Y2C82（Ⅰ、Ⅲ），Y2C84（Ⅰ、Ⅲ），Y2C90（Ⅰ），Y2C92（Ⅰ、Ⅱ）和Y@C82，并确定Y2C2@C82（Ⅲ）和Y2@C82（Ⅲ）的分子结构同属C82-C3v（8）。
Endohedral Metallofullerenes (EMFs) which are different from fullerenes in various properties such as chemical and physical properties, molecule and electrical properties, electronic structures, have a wide range of potential applications in photoelectrochemical materials, magnetic resonance imaging contrast agents, and medical diagnosis. Because of the low yields, various species (e.g., various metals, cage sizes, and symmetries) and difficult purification, these attractive molecules are also not widely or deeply researched.
In this paper, we prepare the soot by classic DC arc discharge with various sources of yttrium, isolate the soot by means of four diverse treatments, and with the help of column chromatographic isolation, we enrich a great quantity of yttrium metallofullerenes. Finally, a series of Y metallofullerenes based on different fullerene cages, i.e. Y2C80(I), Y2C82(I, III), Y2C84(I, III), Y2C90(I), Y2C92(I, II) and Y@C82are successfully isolated by multi-steps HPLC, and we also confirm that the structure of Y2@C82(IIII) is exactly the same as that of Y2C2@C82(III), i.e. C82-C3v (8), detected by MS, Vis-NIR, CV,13C NMR.
引文
[1]H. W. Kroto, R. F. Curl, R. E. Smally, et al. C60Buckminsterfullerene [J]. Nature,1985,318(6042):162.
[2]J. R. Hesth, S. C. O'Brien, R. E. Smally, et al. Lanthanum complexes of spheroidal carbon shells [J]. J. Am. Chem. Soc.,1985,107(25):7779-7780.
[3]F. F. Li, A. Rodriguez-Fortea, J. M. Poblet, et al. Reactivity of Metallic Nitride Endohedral Metallofullerene Anions:Electrochemical Synthesis of a Lu3N@Ih-C80Derivative [J]. J. Am. Chem. Soc,2011,133(8):2760-2765.
[4]N. Chen, C. R. Wang, et al. Comparative Spectroscopic and Reactivity Studies of Sc3-xYxN@C80(x=0-3)[J]. J. Phys. Chem. C,2007,111(32):11823-11828.
[5]F. F. Li, A. L. Balch, Luis Echegoyen, et al.[2+2] Cycloaddition Reaction to Sc3N@Ih-C80The Formation of Very Stable [5,6]-and [6,6]-Adducts [J]. J. Am. Chem. Soc.,2011,133(5):1563-1571.
[6]T. S. Wang, C. R Wang, et al. Spin Divergence Induced by Exohedral Modification:ESR Study of Sc3C2@C80Fulleropyrrolidine [J]. Angew. Chem. Int. Ed.,2010,49(10):1786-1789.
[7]W. D. Cheng, H. Hu, H. Zhang, et al. Effect of Cage Charges on Multiphoton Absorptions:First-Principles Study on Metallofullerenes Sc2C2@C68and Sc3N@C68[J]. J. Phys. Chem. A,2009,113(20):5966-5971.
[8]H. Kurihara, T. Akasaka, S. Nagase, et al. Sc2C2@Cso Rather than Sc2@Cs2: Templated Formation of Unexpected C2v (5)-Cso and Temperature-Dependent Dynamic Motion of Internal Sc2C2Cluster [J]. J. Am. Chem. Soc,2011,133(8):2382-2385.
[9]C. B. Kah, J. Nathaniel, X. Q. Wang, et al. Structural and Electronic Stability of Russian-Doll-Structured Sc4C2@C8o [J]. J. Phys. Chem. C,2010,114(30): 13017-13019.
[10]Z. F. Chen, C. B. Kah, X. Q. Wang, et al. Electronic shell structures of Russian-doll-style Sc4C2@C8o [J]. Chemical Physics Letters,2011,506:230-232.
[11]W. Xu, C. Y. Shu, C. R. Wang, et al. Entrapped Planar Trimetallic Carbide in a Fullerene Cage:Synthesis, Isolation, and Spectroscopic Studies of Lu3C2@C88[J]. J. Phys. Chem. C,2011,115(2):402-405.
[12]B. Q. Mercado, A. L. Balch, et al. A Seven Atom Cluster in a Carbon Cage, The Crystallographically Determined Structure of Sc4(μ3-O)2@Ih-C80[J]. Chem. Commun.,2010,46:279-281.
[13]J. H. Weaver, Y. Chai, G. H. Kroll, et al. XPS Probes of Carbon-Caged Metals [J]. Chem. Phys. Lett.,1992,190(5):460-464.
[14]H. Shinohara, H. Sato, Y. Saito, et al. Mass Spectroscopic and ESR Characterization of Soluble Yttrium-Containing Metallofullerenes YC82and Y2C82[J]. J. Phys. Chem.,1992,96(9):3571-3573.
[15]H. Shinohara, M. Inakuma, M. Kishida, et al. An Oriented Cluster Formation of Endohedral Y@C82Metallofullerenes on Clean Surfaces [J]. J. Phys. Chem.,1995,99(38):13769-13771.
[16]Y F. Lian, Z. J. Shi, X H. Zhou, et al. High-Yield Synthesis of Endohedral Metallofullerenes Y@C2n and Y2@C2n [J]. Chinese. Chemical. Lett,1999,10(5):425-428.
[17]Y. F. Lian, Z. J. Shi, X. H. Zhou, et al. High-yield Preparation of Endohedral Metallofullerenes by an Improved DC Arc-discharge Method [J]. Carbon,2000,38:2117-2121.
[18]Y. F. Lian, Z. J. Shi, X. H. Zhou, et al. Different Extraction Behaviors between Divalent and Trivalent Endohedral Metallofullerenes [J]. Chem. Mater.,2004,16(9).1704-1714.
[19]T. Inoue, T. Tomiyama, T. Sugai, et al. Spectroscopic and Structural Study of Y2C2Carbide Encapsulating Endohedral Metallofullerene:(Y2C2)@C82[J]. Chem. Phys.Lett,2003,382(3-4):226-231.
[20]T. Inoue, T. Tomiyama, T. Sugai, et al. Trapping a C2Radical in Endohedral Metallofullerenes:Synthesis and Structures of (Y2C2)@C82(Isomers I, II, and III)[J]. J. Phys. Chem. B,2004,108(23):7573-7579.
[21]E. Nishibori, S. Narioka, M. Takata, et al. A C2Molecule Entrapped in the Pentagonal-Dodecahedral Y2Cage in Y2C2@C82(III)[J]. ChemPhysChem,2006,7(2):345-348.
[22]G. J. Su, L. H. Gan, C. R. Wang, et al. Dispersion of Metallofullerene Y@C82on Bare, C60-Modified, and Iodine-Modified Au (111) Surfaces Investigated with ECSTM [J]. J. Phys. Chem. B,2006,110(11):5559-5562.
[23]C. C. M., A. Kitaygorodskiy, L. Echegoyen, et al. Trimetallic Nitride Endohedral Metallofullerenes:Reactivity Dictated by the Encapsulated Metal Cluster [J]. J. Am. Chem. Soc,2005,127(29):10448-10453.
[24]N. Chen, E. Y. Zhang, C. R. Wang, et al. C80Encaging Four Different Atoms:The Synthesis, Isolation, and Characterizations of ScYErN@C80[J]. J. Phys. Chem. B,2006,110(27):13322-13325.
[25]T. Zuo, L. Xu, C. M, et al. M2@C79N (M=Y, Tb):Isolation and Characterization of Stable Endohedral Metallofullerenes Exhibiting M-M Bonding Interactions inside Aza[80]fullerene Cages [J]. J. Am. Chem. Soc,2008,130(39):12992-12997.
[26]W. J. Fu, L. Xu, H. Azurmendi, et al.89Y and13C NMR Cluster and Carbon Cage Studies of an Yttrium Metallofullerene Family, Y3N@C2n (n=40-43)[J]. J. Am. Chem. Soc,2009,131(33):11762-11769.
[27]S. Osuna, M. Swart, M. Sola, et al. The Diels-Alder Reaction on Endohedral Y3N@C78:The Importance of the Fullerene Strain Energy [J]. J. Am. Chem. Soc,2009,131(1):129-139.
[28]X. Lu, H. Nikawa, L. Feng, et al. Location of the Yttrium Atom in Y@Cs2and Its Influence on the Reactivity of Cage Carbons [J]. J. Am. Chem. Soc,2009,131(34);12066-12067.
[29]C. Y. Shu, C. R. Wang, H. C. Dorn, et al. Syntheses and Structures of Phenyl-Csi-Butyric Acid Methyl Esters (PCBMs) from M3N@C80[J]. Org. Lett.,2009,11(8):1753-1756.
[30]P. Bharadwaj, L. Novotny. Plasmon-Enhanced Photoemission from a Single Y3N@C80Fullerene [J]. J. Phys. Chem. C,2010,114(16):7444-7447.
[31]A. A. Popov, L. Zhang, L. Dunsch. A Pseudoatom in a Cage:Trimetallofullerene Y3@C80Mimics Y3N@Cso with Nitrogen Substituted by a Pseudoatom [J]. nano,2010,4(2):795-802.
[32](a) W. J. Fu, J. Y. Zhang, H. Champion, et al. Electronic Properties and13C NMR Structural Study of Y3N@C88[J]. Inorg. Chem.,2011,50(10):4256-4259.(b) B. G. Burk, J. Chan, K. A. Williams, et al. Vibrational Spectrum of the Endohedral Y2C2@C92Fullerene by Raman Spectroscopy:Evidence for Tunneling of The Diatomic C2Molecule [J]. Phys. Rev. B,2011,83(11):115457.(c) J. Y. Zhang, T. Fuhrer, W. J. Fu, et al. Nanoscale Fullerene Compression of a Yttrium Carbide Cluster [J]. J. Am. Chem. Soc,2012, Just Accepted.
[33]Y. Zhang, S. Peng, X. J. Li, et al. Structural Stability, Electronegativity and Electronic Property of Endohedral TM@C24and Exohedral TM-C24(TM=Sc, Y and La) Metallofullerene Complexes:Density-functional Theory Investigations [J]. Journal of Molecular Structure:THEOCHEM,2010,947(1-3):16-21.
[34](a)江岸.Sm金属富勒烯的合成、分离、结构和衍生[D].博士论文,浙江大学,2010.(b)卢兴.富勒烯金属包合物的研究[D].博士论文,北京大学,2004.(c)廉永福.富勒烯笼内金属包合物和单层碳纳米管的研究[D].博士论文,北京大学,2000.
[35]W. Krastchmer, L. D. Lamb, K. Fostiropoulos, et al. Solid C60:a New Form of Carbon [J]. Nature,1990,347(6291):354.
[36]M. M. Alvarez, E. G. Gillan, R. B. Kaner, et al. La2@C80:a Soluble Dimetallofullerene [J]. J. Phys. Chem.,1991,95(26):10561-10563.
[37]M. Krause, F. Ziegs, L. Dunsch. Entrapped Bonded Hydrogen in a Fullerene:The Five-atom Cluster Sc3CHin Cso [J]. ChemPhysChem,2007,8(4):537-540.
[38]董金泉,孙宝云,赵宇亮,郝健.自动填料式电弧合成炉[P].中国：102001644A,2011.04.06.
[39](a) Y. Chen, T. R. Ohno, G H. Kroll, et al. Carbon Arc Generation of C60[J]. Materials Research Society,1991,206:627-637.(b)C. Moschel, M. Jansen. ANovel Approach to The Synthesis of Endohedral Fullerenes as Demonstrated by Endohedral Barium Fullerenes [J]. Chem. ber.,1997,130(12):1761-1764.
[40](a) K. Kikuchi, K. Kobayashi, K. Sueki, et al. Encapsulation of Radioactive159Gd and161Tb Atoms in Fullerene Cages [J]. J. Am. Chem. Soc,1994,116(21):9775-9776.(b) K. Sueki, K. Akiyama, K. Kikuchi, et al. AC82Carbon Cage Stable toward Two Different Oxidation States of Endohedral Metal Atoms [J]. J. Phys. Chem. B,1999,103(9):1390-1392.
[41](a) M. Saunders, H. Jimenz-Vazquez, R Cross, et al. Incorporation of Helium, Neon, Argon, Krypton, and Xenon into Fullerenes Using High Pressure [J]. J. Am. Chem. Soc,1994,116(5):2193-2194.(b) M. Saunders, H. Jimenz-Vazquez, R. Cross, et al. Probing The Interior of Fullerenes by3He NMR Spectroscopy of Endohedral3He@C60and3He@C70[J]. Nature,1994,367(6460):256-257.
[42](a) M. Saunders, R Cross, J. Laskin, et al. An NMR Study of He2Inside C70[J]. J. Am. Chem. Soc,1998,120(25):6380-6383.(b) Y. Chai, T. Guo, C. Jin, et al. Fullerenes with Metals Inside [J]. J. Phys. Chem.,1991,95(21):7564-7568.
[43](a) Z. M. Wan, J. F. Christian, S. L. Anderson. Collision of Alkali Ions with C60/C70:Insertion, Theimionic Emission, and Framentaton [J]. J. Chem. Phys.,1993,99(8):5858-5870.(b) T. Ohtsuki, K. Masumoto, Y Kawazoe, et al. Insertion of Be Atom in C60Fullerene Cages:Be@C60[J]. Phys. Rev. Lett,1996,77(17): 3522-3524.(c) H. J Huang, M. Ata, Y. Yoshimoto. Cu@C60Formation in Rrf-plasma and Ring-current Induced Magnetism of C6o [J]. Chem. Commun.,2004,10:1206-1207.(d) W. Xin, X. Lu. Dimetalloendofullerene U2@C60has a U-U Multiple Bond Consisting of Six Fold One Electron Two Center Bonds [J]. J. Am. Chem. Soc,2007,129(7):2171-2177.
[44]D. Roy, N. K. Tripathi, A. Saraiya, et al. Modification of Conductivity of P3HT by Addition of Endometallo Fullerene [J]. Journal of Applied Polymer Science,2009,114(1):491-495.
[45]M. D. Diener, J. M. Alford. Isolation and Properties of Small Bandgap Fullerenes [J]. Nature,1998,393(6686):668-671.
[46]R. D. Bolskar, M. J. Alford. Chemical Oxidation of Endohedral Metallo-fullerenes:Identification and Separation of Distinct Classes [J]. Chem. Commun.,2003,11:1292-1293.
[47]B. Y. Sun, Z. N. Gu. Solvent Dependent Anion Studies on Enrichment of Metallofullerene [J]. Chemistry Letters,2002,31(12):1164.
[48]B. Y. Sun, L. Feng, Z. J. Shi, etal. Improved Extraction of Metallofullerenes with DMF at High Temperature [J]. Carbon,2002,40:1591.
[49]H. J. Huang, S. H. Yang. Toward Efficient Synthesis of Endohedral Metallo-fullerenes by Arc Discharge of Carbon Rods Containing Encapsulated Rare Earth Carbides and Ultrasonic Soxhlet Extraction [J]. Chem. Mater.,2000,12(9):2715-2720.
[50]D. Y. Sun, Z. Y. Liu, X. H Guo, et al. High-yield Extraction of Endohedral Rare-earth Fullerene [J]. J. Phys. Chem. B,1997,101(20):3927-3930.
[51]J. Q. Ding, S. H. Yang. Efficient N, N-dimethylformamide Extraction of Endohedral Metallofullerenes for HPLC Purification [J]. Chem. Mater.,1996,8(12):2824-2827.
[52]B. Y Sun, T. Inoue, T. Shimada, et al. Synthesis and Characterization of Eu-metallofullerenes from Eu@C74to Eu@C9o and their Nanopeapds [J]. J. Phys. Chem. B,2004,108(26):9011-9015.
[53]K. Fuchs, H. Rietschel, R. H. Michael, et al. Extraction and Chromatographic Elution Behavior of Endohedral Metallofullerenes:Inferences Regarding Effective Dipole Moments [J]. J. Phys. Chem.,1996,100(2):725-729.
[54]H. Huang, S. Yang. Relative Yields of Endohedral Lanthanide Metallofullerenes by Arc Synthesis and Their Correlation with the Elution Behavior [J]. J. Phys. Chem. B,1998,102(50):10196-10200.
[55]K. Sueki, K. Akiyama, Y. Zhao, et al. Systematic Study of Lanthanoid Endohedral Metallofullerenes:Production Yields, HPLC Retention Time and Reactor Irradiation Effects [J]. J. Radio analytical and Nucl. Chem.,2003,255:159-164.
[56]X. Z. Nakane, H Shinohara. Production and Isolaion of Ca@C82(I-IV) and Ca@C84(I, II Metallofullerenes [J]. J. Am. Chem. Soc.,1996,118(45):11309-11310.
[57]S.M. Grannan, J. T. Birmingham, P. L. Richards, et al. Infrared Transmittance of Sc2@C84and Er2@C82[J]. Chem. Phys. Lett,1997,264:359-365.
[58]K. Akiyama, K. Sueki, T. Kodama, et al. Absorption Spectra of Metallofullerenes M@C82ofLanthanoids [J]. J. Phys. Chem. A,2000,104(31):7224-7226.
[59]M. Inakuma, E. Yamamoto, T. Ka, et al. Structural and Electronic Properties of Isomers of Sc2@C84(I,II,III):13CNMR and IR/Raman Spectroscopic Studies [J]. J. Phys. Chem. B,2000,104(21):5072-5077.
[60]R Johnson, J. Salem, D. Bethune, et al. Electron Paramagnetic Resonance Studies of Lanthanum-Containing C82[J]. Nature,1992,355(6357):239.
[61]H. Shinohara, H. Sato, M. Ohkohchi, et al. Encapsulation of a Scandium Trimer in C82[J]. Nature,1992,357(6373):52-54.
[62]S. Suzuki, S. Kawata, H. Shiromaru, et al. Isomers and Carbon-13Hyperfine Structures of Metal-encapsulated Fullerenes M@Cs2(M=Sc, Y, and La)[J]. J. Phys. Chem.,1992,96(18):7159-7161.
[63]H. Funasaka, K. Sugiyama, K. Yamamoto, et al. Magnetic Properties of Rare Earth Metallofullerenes [J]. J. Phys. Chem.,1995,99(7):1826-1830.
[64]M. Inakuma, H. isanori Shinohara. Temperature-Dependent EPR Studies on Isolated Scandium Metallofullerenes:Sc@C82(I, II) and Sc@C84[J]. J. Phys. Chem. B,2000,104(32):7595-7599.
[65]A. A. Popov, L. Dunsch. Hindered Cluster Rotation and45Sc Hyperfine SplittingConstant in Distonoid Anion Radical Sc3N@C80, and Spatial Spin-Charge Separation as a General Principle for Anions of Endohedral Fullerenes with Metal-Localized Lowest Unoccupied Molecular Orbitals [J]. J. Am. Chem. Soc.,2008,130(52),17726-17742.
[66]X. Lu, H. Nikawa, T. Tsuchiya, et al. Nitrated Benzyne Derivatives of La@C82Addition of NO2and Its Positional Directing Effect on the Subsequent Addition of Benzynes [J]. Angew. Chem. Int. Ed.,2010,49(3):594-597.
[67]J. J. Yin, F. Lao, B. Y. Sun, et al. The Scavenging of Reactive Oxygen Species and The Potential for Cell Protection by Functionalized Fullerene Materials [J]. Biomaterials,2009,30:611-621.
[68]E. Yamamoto, M. Tansho, T. Tomiyama, et al.13C NMR Study on The Structure of Isolated Sc2@C84Metallofullerene [J]. J. Am. Chem. Soc.,1996,118(9):2293-2294.
[69]S. Nagase, K Kobayashi. Theoretical Study of The Lanthanide Fullerene CeC82Comparison with ScC82, YC82and LaC82[J]. Chem. Phys. Lett,1994,228(1-3):106-110.
[70]C. R. Wang, T. Kai, T. Yoshida, et al. C66Fullerene Encaging a Scandium Ddimmer [J]. Nature,2000,408(6811):426.
[71]H. Kato, T. Sugai, H. Shinohara, et al. Structure of a Missing-Caged Metallofullerene:La@C72[J]. J. Am. Chem. Soc.,2003,125(26):7782-7783.
[72]T. Akasak, T. Wakahara, S. Nagase, et al. Structural Determination of The La@C82Isomer [J]. J Phys. Chem. B,2001,105(15):2971-2974.
[73]B. P. Cao, T. Akasaka, K. Kobayash, et al. Isolation, Characterization, and Theoretical Study ofLa2@C78[J]. J. Am. Chem. Soc,2004,126(30):9164-9165.
[74]M. Yamada, T. Akasaka, S. Nagase, et al. Location of The Metal Atoms in Ce2@C78and Its Bissilylated Derivative [J]. Chem. Commun.,2008,5:558-560.
[75]M. Yamada, T. Akasaka, S. Nagase, et al. Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage:Ce2@C72[J]. J. Phys. Chem. A,2008,112(33):7627-7631.
[76]Y. Takano., T. Akasaka., T. Kato., et al. Anisotropic Magnetic Behavior of Anionic Ce@C82Carbene Adducts [J]. J. Am. Chem. Soc,2009,131(26):9340-9346.
[77]M. M. Olmstead, S. Stevenson, H. C. Dorn, et al. Isolation and Structural Characterization of The Endohedral Fullerene Sc3N@C78[J]. Angew. Chem. Int. Ed,2001,40(7):1223-1125.
[78]S. Stevenson, E. Hadju, R. Bible, et al. Small-band Gap Endohedral Metallofullerenes in Highyield and Purity [J]. Nature,1999,401(6748):55-56.
[79]T. Cai, L. S. Xu, M. R. Anderson, et al. Structure and Enhanced Reaetivity Rates of The D5h Sc3N@C8o and Lu3N@C80Etallofullerene Isomers:The Importance of The Pyracylene Motif [J]. J. Am. Chem. Soc,2006,128(26):8581-8589.
[80]T. M. Zuo, C. M. Beavers, H. C. Dorn, et al. Isolation and Structural Characterization of a Family of Endohedral Fullerenes Including The Large, Chiral Cage Fullerenes Tb3N@C88and Tb3N@C86as well as The Ih and Dsh Isomers of Tb3N@C80[J]. J. Am. Chem. Soc,2007,129(7):2035-2043.
[81]M. M. Olmstead, S. Stevenson, H. C. Dorn, et al. Sc3N@C68:Folded Pentalene Coordination in an Endohedral Fullerene that Does not Obey the Isolated Pentagon Rule [J]. Angew. Chem. Int. Ed.,2003,42(8):900-903.
[82]C. M. Beavers, M. M. Olmstead, A. L. Balch, et al. Large Metal Ions in a Relatively Small Fullerene Cage:the Structure of Gd3N@C2(22010)-C78Departs from the Isolated Pentagon Rule [J]. J. Am. Chem. Soc,2009,131(32):11519-11524.
[83]B. Q. Mereado, C. M. Beavers, M. M. Olmstead, et al. Is the Isolated Pentagon Rule Merely a Suggestion for Endohedral Fullerenes? The Structure of a Second Egg-Shaped Endohedral Fullerenes Gd3N@Cs (39663)-C82[J]. J. Am. Chem. Soc,2008,130(25):7854-7855.
[84](a)C. M. Beavers, M. M. Olmstead, H. C. Dorn, et al. Tb3N@C84:an Improble, Egg-Shaped Endohedral Fullerene That Violates The Isolated Pentagon Rule [J]. J. Am. Chem. Soc,2006,128(35):11352-11353.(b) T. M. Zuo, K. Walker, M. M. Olmstead, et al. New Egg-Shaped Endohedral Fullerene:Non-Isolated Pentagon Structures of Tm3N@Cs (51365)-C84and Gd3N@Cs (51365)-C84[J]. Chem. Commun,2008,9:1067-1069.
[85]X. Lu, Y. F. Lian, C. M. Beavers, et al. Crystallographic X-ray Analyses of Yb@C2v (3)-C8o Reveal a Feasible Rule That Governs the Location of a Rare Earth Metal inside a Medium-Sized Fullerene[J]. J. Am. Chem. Soc.,2011,133(28):10772-10775.
[86]H. Shinohara, N. Hayashi, H. Sato, et al. Direct STM Imaging of Spherical Endohedral Discandium Fullerenes (Sc2@C84)[J]. J. Phys. Chem.,1993,97(51):13438-13440.
[87]X. Wang, T. Hashizume, H. Shinohara, et al. Scanning Tunneling Microscopy of C60on the Si (111)7x7Surface [J]. J. Appl. Phys.,1992,31(7B):L983-L986.
[88]B. Shi, X. Wang, H. Huang, et al. Scanning Tunneling Microscopy of Endohedral Metallofullerene Tb@C82on C60Film and Si (100)2x1Surface [J]. J. Phys. Chem. B,2001,105(46):11414-11418.
[89]A. Taninaka, K. Shino, T. Sugai, et al. Scanning Tunneling Microscopy Spectroscopy Studies of Lanthanum Endohedral Metallofullerenes [J]. Nano Lett.,2003,3:337-341.
[90]S. X. Zhao, J. Hao, B. Y. Sun, et al. Scanning Tunneling Microscopy Investigation of Substrate-Dependent Adsorption and Assembly of Metallofullerene Gd@C82on Cu (111) and Cu (100)[J]. J. Phys. Chem. C,2011,115(14):6265-6268.
[91]Y. Takano, S. Nagase, T. Akasaka, et al. Donor-Acceptor Conjugates of Lanthanum Endohedral Metallofullerene and π-Extended Tetrathiafulvalene [J]. J. Am. Chem. Soc.,2010,132(23):8048-8055.
[92]M. O.Ishitsuka, T. Akasaka, S. Nagase, et al. Regio selective Bis-functionalization of Endohedral Dimetallofullerene, La2@C8o:Extremal La-La Distance [J]. J. Am. Chem. Soc,2011,133(18):7128-7134.
[93]T.Yang, X.Zhao, S.Nagase, et al. Di-lanthanide Encapsulated into Large Fullerene Cioo:a DFT Surveyw [J]. Phys. Chem. Chem. Phys.,2011,13(11):5034-5037.
[94]J. Y. Wang, C. S.Lin, M. Y. Zhang, et al. Effect of Cage Size on the Third-Order Optical Properties of Endohedral Metallofullerenes Sc3N@C2n (2n=68,70,78, and80):A Theoretical Study [J]. International Journal of Quantum Chemistry,2012,112(3):759-769.
[95](a) F. F. Li, A. Rodriguez-Fortea, J. M. Poblet, et al. Reactivity of Metallic Nitride Endohedral Metallofullerene Anions:Electrochemical Synthesis of a Lu3N@Ih-C80Derivative [J]. J. Am. Chem. Soc.,2011,133(8):2760-2765.(b) B. Yang, R. F. Peng, B. Jin, et al. Preparation and Characterization of Langmuir-Blodgett Films of Endohedral Metallofullerene Gd@Cs2[J]. Synthetic Metals.,2011,161(9-10):770-774.
[96](a) X. Li, T. E. Yankeelov, G. D. Rosen, et al. Enhancement of Histological Volumes Through Averaging and Their Use for The Analysis of Magnetic Resonance Images [J]. Magnetic Resonance Imaging.,2009,27(3):401-416.(b) J. F. Zhang, P. P. Fatouros, C. Y. Shu, et al. High Relaxivity Trimetallic Nitride (Gd3N) Metallo-fullerene MRI Contrast Agents with Optimized Functionality [J]. Bioconjugate Chem.,2010,21(4):610-615.
[97](a)王晨.钇内嵌金属富勒烯制备与分离[D].硕士论文,黑龙江大学,2010.(b)王冲.Yb金属富勒烯包合物及特殊结构富勒烯的研究[D].硕士论文,大连理工大学,2007.(c)陈传宝.含金属钛的新型内嵌富勒烯的合成,分离及性质研究[D].博士论文,中国科学技术大学,2011.
[98]S. F. Yang, L. Z. Fan, S. H. Yang. Significantly Enhanced Photocurrent Efficiency of a Poly (3-hexylthiophene) Photoelectrochemical Device by Doping with The Endohedral Metallofullerene Dy@C82[J]. Chem. Phys. Lett.,2004,388(4-6):253-258.
[99]J. Tang, G. M. Xing, Y. L. Zhao. Switchable Semiconductive Property of the Polyhydroxylated Metallofullerene [J]. J. Phys. Chem. B,2007,111(41):11929-11934.
[100]J. R. Pinzon, C. M. Cardona, M. A. Herranz. Metal Nitride Cluster Fullerene M3N@C80(M=Y, Sc) Based Dyads:Synthesis, and Electrochemical, Theoretical and Photophysical Studies [J]. Chem. Eur. J.,2009,15(4):864-877.
[101]M. Yamada, N. Mizorogi, T. Tsuchiya, et al. Synthesis and Characterization of the D5h Isomer of the Endohedral Dimetallofullerene Ce2@C80:Two-Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage [J]. Chem. Eur. J.,2009,15(37):9486-9493.
[102]D. M Guldi, L. Feng, S. G. Radhakrishnan, et al. A Molecular Ce2@Ih-C80Switchs Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity [J]. J. Am. Chem. Soc,2010,132(26):9078-9086.
[2]J. R. Hesth, S. C. O'Brien, R. E. Smally, et al. Lanthanum complexes of spheroidal carbon shells [J]. J. Am. Chem. Soc.,1985,107(25):7779-7780.
[3]F. F. Li, A. Rodriguez-Fortea, J. M. Poblet, et al. Reactivity of Metallic Nitride Endohedral Metallofullerene Anions:Electrochemical Synthesis of a Lu3N@Ih-C80Derivative [J]. J. Am. Chem. Soc,2011,133(8):2760-2765.
[4]N. Chen, C. R. Wang, et al. Comparative Spectroscopic and Reactivity Studies of Sc3-xYxN@C80(x=0-3)[J]. J. Phys. Chem. C,2007,111(32):11823-11828.
[5]F. F. Li, A. L. Balch, Luis Echegoyen, et al.[2+2] Cycloaddition Reaction to Sc3N@Ih-C80The Formation of Very Stable [5,6]-and [6,6]-Adducts [J]. J. Am. Chem. Soc.,2011,133(5):1563-1571.
[6]T. S. Wang, C. R Wang, et al. Spin Divergence Induced by Exohedral Modification:ESR Study of Sc3C2@C80Fulleropyrrolidine [J]. Angew. Chem. Int. Ed.,2010,49(10):1786-1789.
[7]W. D. Cheng, H. Hu, H. Zhang, et al. Effect of Cage Charges on Multiphoton Absorptions:First-Principles Study on Metallofullerenes Sc2C2@C68and Sc3N@C68[J]. J. Phys. Chem. A,2009,113(20):5966-5971.
[8]H. Kurihara, T. Akasaka, S. Nagase, et al. Sc2C2@Cso Rather than Sc2@Cs2: Templated Formation of Unexpected C2v (5)-Cso and Temperature-Dependent Dynamic Motion of Internal Sc2C2Cluster [J]. J. Am. Chem. Soc,2011,133(8):2382-2385.
[9]C. B. Kah, J. Nathaniel, X. Q. Wang, et al. Structural and Electronic Stability of Russian-Doll-Structured Sc4C2@C8o [J]. J. Phys. Chem. C,2010,114(30): 13017-13019.
[10]Z. F. Chen, C. B. Kah, X. Q. Wang, et al. Electronic shell structures of Russian-doll-style Sc4C2@C8o [J]. Chemical Physics Letters,2011,506:230-232.
[11]W. Xu, C. Y. Shu, C. R. Wang, et al. Entrapped Planar Trimetallic Carbide in a Fullerene Cage:Synthesis, Isolation, and Spectroscopic Studies of Lu3C2@C88[J]. J. Phys. Chem. C,2011,115(2):402-405.
[12]B. Q. Mercado, A. L. Balch, et al. A Seven Atom Cluster in a Carbon Cage, The Crystallographically Determined Structure of Sc4(μ3-O)2@Ih-C80[J]. Chem. Commun.,2010,46:279-281.
[13]J. H. Weaver, Y. Chai, G. H. Kroll, et al. XPS Probes of Carbon-Caged Metals [J]. Chem. Phys. Lett.,1992,190(5):460-464.
[14]H. Shinohara, H. Sato, Y. Saito, et al. Mass Spectroscopic and ESR Characterization of Soluble Yttrium-Containing Metallofullerenes YC82and Y2C82[J]. J. Phys. Chem.,1992,96(9):3571-3573.
[15]H. Shinohara, M. Inakuma, M. Kishida, et al. An Oriented Cluster Formation of Endohedral Y@C82Metallofullerenes on Clean Surfaces [J]. J. Phys. Chem.,1995,99(38):13769-13771.
[16]Y F. Lian, Z. J. Shi, X H. Zhou, et al. High-Yield Synthesis of Endohedral Metallofullerenes Y@C2n and Y2@C2n [J]. Chinese. Chemical. Lett,1999,10(5):425-428.
[17]Y. F. Lian, Z. J. Shi, X. H. Zhou, et al. High-yield Preparation of Endohedral Metallofullerenes by an Improved DC Arc-discharge Method [J]. Carbon,2000,38:2117-2121.
[18]Y. F. Lian, Z. J. Shi, X. H. Zhou, et al. Different Extraction Behaviors between Divalent and Trivalent Endohedral Metallofullerenes [J]. Chem. Mater.,2004,16(9).1704-1714.
[19]T. Inoue, T. Tomiyama, T. Sugai, et al. Spectroscopic and Structural Study of Y2C2Carbide Encapsulating Endohedral Metallofullerene:(Y2C2)@C82[J]. Chem. Phys.Lett,2003,382(3-4):226-231.
[20]T. Inoue, T. Tomiyama, T. Sugai, et al. Trapping a C2Radical in Endohedral Metallofullerenes:Synthesis and Structures of (Y2C2)@C82(Isomers I, II, and III)[J]. J. Phys. Chem. B,2004,108(23):7573-7579.
[21]E. Nishibori, S. Narioka, M. Takata, et al. A C2Molecule Entrapped in the Pentagonal-Dodecahedral Y2Cage in Y2C2@C82(III)[J]. ChemPhysChem,2006,7(2):345-348.
[22]G. J. Su, L. H. Gan, C. R. Wang, et al. Dispersion of Metallofullerene Y@C82on Bare, C60-Modified, and Iodine-Modified Au (111) Surfaces Investigated with ECSTM [J]. J. Phys. Chem. B,2006,110(11):5559-5562.
[23]C. C. M., A. Kitaygorodskiy, L. Echegoyen, et al. Trimetallic Nitride Endohedral Metallofullerenes:Reactivity Dictated by the Encapsulated Metal Cluster [J]. J. Am. Chem. Soc,2005,127(29):10448-10453.
[24]N. Chen, E. Y. Zhang, C. R. Wang, et al. C80Encaging Four Different Atoms:The Synthesis, Isolation, and Characterizations of ScYErN@C80[J]. J. Phys. Chem. B,2006,110(27):13322-13325.
[25]T. Zuo, L. Xu, C. M, et al. M2@C79N (M=Y, Tb):Isolation and Characterization of Stable Endohedral Metallofullerenes Exhibiting M-M Bonding Interactions inside Aza[80]fullerene Cages [J]. J. Am. Chem. Soc,2008,130(39):12992-12997.
[26]W. J. Fu, L. Xu, H. Azurmendi, et al.89Y and13C NMR Cluster and Carbon Cage Studies of an Yttrium Metallofullerene Family, Y3N@C2n (n=40-43)[J]. J. Am. Chem. Soc,2009,131(33):11762-11769.
[27]S. Osuna, M. Swart, M. Sola, et al. The Diels-Alder Reaction on Endohedral Y3N@C78:The Importance of the Fullerene Strain Energy [J]. J. Am. Chem. Soc,2009,131(1):129-139.
[28]X. Lu, H. Nikawa, L. Feng, et al. Location of the Yttrium Atom in Y@Cs2and Its Influence on the Reactivity of Cage Carbons [J]. J. Am. Chem. Soc,2009,131(34);12066-12067.
[29]C. Y. Shu, C. R. Wang, H. C. Dorn, et al. Syntheses and Structures of Phenyl-Csi-Butyric Acid Methyl Esters (PCBMs) from M3N@C80[J]. Org. Lett.,2009,11(8):1753-1756.
[30]P. Bharadwaj, L. Novotny. Plasmon-Enhanced Photoemission from a Single Y3N@C80Fullerene [J]. J. Phys. Chem. C,2010,114(16):7444-7447.
[31]A. A. Popov, L. Zhang, L. Dunsch. A Pseudoatom in a Cage:Trimetallofullerene Y3@C80Mimics Y3N@Cso with Nitrogen Substituted by a Pseudoatom [J]. nano,2010,4(2):795-802.
[32](a) W. J. Fu, J. Y. Zhang, H. Champion, et al. Electronic Properties and13C NMR Structural Study of Y3N@C88[J]. Inorg. Chem.,2011,50(10):4256-4259.(b) B. G. Burk, J. Chan, K. A. Williams, et al. Vibrational Spectrum of the Endohedral Y2C2@C92Fullerene by Raman Spectroscopy:Evidence for Tunneling of The Diatomic C2Molecule [J]. Phys. Rev. B,2011,83(11):115457.(c) J. Y. Zhang, T. Fuhrer, W. J. Fu, et al. Nanoscale Fullerene Compression of a Yttrium Carbide Cluster [J]. J. Am. Chem. Soc,2012, Just Accepted.
[33]Y. Zhang, S. Peng, X. J. Li, et al. Structural Stability, Electronegativity and Electronic Property of Endohedral TM@C24and Exohedral TM-C24(TM=Sc, Y and La) Metallofullerene Complexes:Density-functional Theory Investigations [J]. Journal of Molecular Structure:THEOCHEM,2010,947(1-3):16-21.
[34](a)江岸.Sm金属富勒烯的合成、分离、结构和衍生[D].博士论文,浙江大学,2010.(b)卢兴.富勒烯金属包合物的研究[D].博士论文,北京大学,2004.(c)廉永福.富勒烯笼内金属包合物和单层碳纳米管的研究[D].博士论文,北京大学,2000.
[35]W. Krastchmer, L. D. Lamb, K. Fostiropoulos, et al. Solid C60:a New Form of Carbon [J]. Nature,1990,347(6291):354.
[36]M. M. Alvarez, E. G. Gillan, R. B. Kaner, et al. La2@C80:a Soluble Dimetallofullerene [J]. J. Phys. Chem.,1991,95(26):10561-10563.
[37]M. Krause, F. Ziegs, L. Dunsch. Entrapped Bonded Hydrogen in a Fullerene:The Five-atom Cluster Sc3CHin Cso [J]. ChemPhysChem,2007,8(4):537-540.
[38]董金泉,孙宝云,赵宇亮,郝健.自动填料式电弧合成炉[P].中国：102001644A,2011.04.06.
[39](a) Y. Chen, T. R. Ohno, G H. Kroll, et al. Carbon Arc Generation of C60[J]. Materials Research Society,1991,206:627-637.(b)C. Moschel, M. Jansen. ANovel Approach to The Synthesis of Endohedral Fullerenes as Demonstrated by Endohedral Barium Fullerenes [J]. Chem. ber.,1997,130(12):1761-1764.
[40](a) K. Kikuchi, K. Kobayashi, K. Sueki, et al. Encapsulation of Radioactive159Gd and161Tb Atoms in Fullerene Cages [J]. J. Am. Chem. Soc,1994,116(21):9775-9776.(b) K. Sueki, K. Akiyama, K. Kikuchi, et al. AC82Carbon Cage Stable toward Two Different Oxidation States of Endohedral Metal Atoms [J]. J. Phys. Chem. B,1999,103(9):1390-1392.
[41](a) M. Saunders, H. Jimenz-Vazquez, R Cross, et al. Incorporation of Helium, Neon, Argon, Krypton, and Xenon into Fullerenes Using High Pressure [J]. J. Am. Chem. Soc,1994,116(5):2193-2194.(b) M. Saunders, H. Jimenz-Vazquez, R. Cross, et al. Probing The Interior of Fullerenes by3He NMR Spectroscopy of Endohedral3He@C60and3He@C70[J]. Nature,1994,367(6460):256-257.
[42](a) M. Saunders, R Cross, J. Laskin, et al. An NMR Study of He2Inside C70[J]. J. Am. Chem. Soc,1998,120(25):6380-6383.(b) Y. Chai, T. Guo, C. Jin, et al. Fullerenes with Metals Inside [J]. J. Phys. Chem.,1991,95(21):7564-7568.
[43](a) Z. M. Wan, J. F. Christian, S. L. Anderson. Collision of Alkali Ions with C60/C70:Insertion, Theimionic Emission, and Framentaton [J]. J. Chem. Phys.,1993,99(8):5858-5870.(b) T. Ohtsuki, K. Masumoto, Y Kawazoe, et al. Insertion of Be Atom in C60Fullerene Cages:Be@C60[J]. Phys. Rev. Lett,1996,77(17): 3522-3524.(c) H. J Huang, M. Ata, Y. Yoshimoto. Cu@C60Formation in Rrf-plasma and Ring-current Induced Magnetism of C6o [J]. Chem. Commun.,2004,10:1206-1207.(d) W. Xin, X. Lu. Dimetalloendofullerene U2@C60has a U-U Multiple Bond Consisting of Six Fold One Electron Two Center Bonds [J]. J. Am. Chem. Soc,2007,129(7):2171-2177.
[44]D. Roy, N. K. Tripathi, A. Saraiya, et al. Modification of Conductivity of P3HT by Addition of Endometallo Fullerene [J]. Journal of Applied Polymer Science,2009,114(1):491-495.
[45]M. D. Diener, J. M. Alford. Isolation and Properties of Small Bandgap Fullerenes [J]. Nature,1998,393(6686):668-671.
[46]R. D. Bolskar, M. J. Alford. Chemical Oxidation of Endohedral Metallo-fullerenes:Identification and Separation of Distinct Classes [J]. Chem. Commun.,2003,11:1292-1293.
[47]B. Y. Sun, Z. N. Gu. Solvent Dependent Anion Studies on Enrichment of Metallofullerene [J]. Chemistry Letters,2002,31(12):1164.
[48]B. Y. Sun, L. Feng, Z. J. Shi, etal. Improved Extraction of Metallofullerenes with DMF at High Temperature [J]. Carbon,2002,40:1591.
[49]H. J. Huang, S. H. Yang. Toward Efficient Synthesis of Endohedral Metallo-fullerenes by Arc Discharge of Carbon Rods Containing Encapsulated Rare Earth Carbides and Ultrasonic Soxhlet Extraction [J]. Chem. Mater.,2000,12(9):2715-2720.
[50]D. Y. Sun, Z. Y. Liu, X. H Guo, et al. High-yield Extraction of Endohedral Rare-earth Fullerene [J]. J. Phys. Chem. B,1997,101(20):3927-3930.
[51]J. Q. Ding, S. H. Yang. Efficient N, N-dimethylformamide Extraction of Endohedral Metallofullerenes for HPLC Purification [J]. Chem. Mater.,1996,8(12):2824-2827.
[52]B. Y Sun, T. Inoue, T. Shimada, et al. Synthesis and Characterization of Eu-metallofullerenes from Eu@C74to Eu@C9o and their Nanopeapds [J]. J. Phys. Chem. B,2004,108(26):9011-9015.
[53]K. Fuchs, H. Rietschel, R. H. Michael, et al. Extraction and Chromatographic Elution Behavior of Endohedral Metallofullerenes:Inferences Regarding Effective Dipole Moments [J]. J. Phys. Chem.,1996,100(2):725-729.
[54]H. Huang, S. Yang. Relative Yields of Endohedral Lanthanide Metallofullerenes by Arc Synthesis and Their Correlation with the Elution Behavior [J]. J. Phys. Chem. B,1998,102(50):10196-10200.
[55]K. Sueki, K. Akiyama, Y. Zhao, et al. Systematic Study of Lanthanoid Endohedral Metallofullerenes:Production Yields, HPLC Retention Time and Reactor Irradiation Effects [J]. J. Radio analytical and Nucl. Chem.,2003,255:159-164.
[56]X. Z. Nakane, H Shinohara. Production and Isolaion of Ca@C82(I-IV) and Ca@C84(I, II Metallofullerenes [J]. J. Am. Chem. Soc.,1996,118(45):11309-11310.
[57]S.M. Grannan, J. T. Birmingham, P. L. Richards, et al. Infrared Transmittance of Sc2@C84and Er2@C82[J]. Chem. Phys. Lett,1997,264:359-365.
[58]K. Akiyama, K. Sueki, T. Kodama, et al. Absorption Spectra of Metallofullerenes M@C82ofLanthanoids [J]. J. Phys. Chem. A,2000,104(31):7224-7226.
[59]M. Inakuma, E. Yamamoto, T. Ka, et al. Structural and Electronic Properties of Isomers of Sc2@C84(I,II,III):13CNMR and IR/Raman Spectroscopic Studies [J]. J. Phys. Chem. B,2000,104(21):5072-5077.
[60]R Johnson, J. Salem, D. Bethune, et al. Electron Paramagnetic Resonance Studies of Lanthanum-Containing C82[J]. Nature,1992,355(6357):239.
[61]H. Shinohara, H. Sato, M. Ohkohchi, et al. Encapsulation of a Scandium Trimer in C82[J]. Nature,1992,357(6373):52-54.
[62]S. Suzuki, S. Kawata, H. Shiromaru, et al. Isomers and Carbon-13Hyperfine Structures of Metal-encapsulated Fullerenes M@Cs2(M=Sc, Y, and La)[J]. J. Phys. Chem.,1992,96(18):7159-7161.
[63]H. Funasaka, K. Sugiyama, K. Yamamoto, et al. Magnetic Properties of Rare Earth Metallofullerenes [J]. J. Phys. Chem.,1995,99(7):1826-1830.
[64]M. Inakuma, H. isanori Shinohara. Temperature-Dependent EPR Studies on Isolated Scandium Metallofullerenes:Sc@C82(I, II) and Sc@C84[J]. J. Phys. Chem. B,2000,104(32):7595-7599.
[65]A. A. Popov, L. Dunsch. Hindered Cluster Rotation and45Sc Hyperfine SplittingConstant in Distonoid Anion Radical Sc3N@C80, and Spatial Spin-Charge Separation as a General Principle for Anions of Endohedral Fullerenes with Metal-Localized Lowest Unoccupied Molecular Orbitals [J]. J. Am. Chem. Soc.,2008,130(52),17726-17742.
[66]X. Lu, H. Nikawa, T. Tsuchiya, et al. Nitrated Benzyne Derivatives of La@C82Addition of NO2and Its Positional Directing Effect on the Subsequent Addition of Benzynes [J]. Angew. Chem. Int. Ed.,2010,49(3):594-597.
[67]J. J. Yin, F. Lao, B. Y. Sun, et al. The Scavenging of Reactive Oxygen Species and The Potential for Cell Protection by Functionalized Fullerene Materials [J]. Biomaterials,2009,30:611-621.
[68]E. Yamamoto, M. Tansho, T. Tomiyama, et al.13C NMR Study on The Structure of Isolated Sc2@C84Metallofullerene [J]. J. Am. Chem. Soc.,1996,118(9):2293-2294.
[69]S. Nagase, K Kobayashi. Theoretical Study of The Lanthanide Fullerene CeC82Comparison with ScC82, YC82and LaC82[J]. Chem. Phys. Lett,1994,228(1-3):106-110.
[70]C. R. Wang, T. Kai, T. Yoshida, et al. C66Fullerene Encaging a Scandium Ddimmer [J]. Nature,2000,408(6811):426.
[71]H. Kato, T. Sugai, H. Shinohara, et al. Structure of a Missing-Caged Metallofullerene:La@C72[J]. J. Am. Chem. Soc.,2003,125(26):7782-7783.
[72]T. Akasak, T. Wakahara, S. Nagase, et al. Structural Determination of The La@C82Isomer [J]. J Phys. Chem. B,2001,105(15):2971-2974.
[73]B. P. Cao, T. Akasaka, K. Kobayash, et al. Isolation, Characterization, and Theoretical Study ofLa2@C78[J]. J. Am. Chem. Soc,2004,126(30):9164-9165.
[74]M. Yamada, T. Akasaka, S. Nagase, et al. Location of The Metal Atoms in Ce2@C78and Its Bissilylated Derivative [J]. Chem. Commun.,2008,5:558-560.
[75]M. Yamada, T. Akasaka, S. Nagase, et al. Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage:Ce2@C72[J]. J. Phys. Chem. A,2008,112(33):7627-7631.
[76]Y. Takano., T. Akasaka., T. Kato., et al. Anisotropic Magnetic Behavior of Anionic Ce@C82Carbene Adducts [J]. J. Am. Chem. Soc,2009,131(26):9340-9346.
[77]M. M. Olmstead, S. Stevenson, H. C. Dorn, et al. Isolation and Structural Characterization of The Endohedral Fullerene Sc3N@C78[J]. Angew. Chem. Int. Ed,2001,40(7):1223-1125.
[78]S. Stevenson, E. Hadju, R. Bible, et al. Small-band Gap Endohedral Metallofullerenes in Highyield and Purity [J]. Nature,1999,401(6748):55-56.
[79]T. Cai, L. S. Xu, M. R. Anderson, et al. Structure and Enhanced Reaetivity Rates of The D5h Sc3N@C8o and Lu3N@C80Etallofullerene Isomers:The Importance of The Pyracylene Motif [J]. J. Am. Chem. Soc,2006,128(26):8581-8589.
[80]T. M. Zuo, C. M. Beavers, H. C. Dorn, et al. Isolation and Structural Characterization of a Family of Endohedral Fullerenes Including The Large, Chiral Cage Fullerenes Tb3N@C88and Tb3N@C86as well as The Ih and Dsh Isomers of Tb3N@C80[J]. J. Am. Chem. Soc,2007,129(7):2035-2043.
[81]M. M. Olmstead, S. Stevenson, H. C. Dorn, et al. Sc3N@C68:Folded Pentalene Coordination in an Endohedral Fullerene that Does not Obey the Isolated Pentagon Rule [J]. Angew. Chem. Int. Ed.,2003,42(8):900-903.
[82]C. M. Beavers, M. M. Olmstead, A. L. Balch, et al. Large Metal Ions in a Relatively Small Fullerene Cage:the Structure of Gd3N@C2(22010)-C78Departs from the Isolated Pentagon Rule [J]. J. Am. Chem. Soc,2009,131(32):11519-11524.
[83]B. Q. Mereado, C. M. Beavers, M. M. Olmstead, et al. Is the Isolated Pentagon Rule Merely a Suggestion for Endohedral Fullerenes? The Structure of a Second Egg-Shaped Endohedral Fullerenes Gd3N@Cs (39663)-C82[J]. J. Am. Chem. Soc,2008,130(25):7854-7855.
[84](a)C. M. Beavers, M. M. Olmstead, H. C. Dorn, et al. Tb3N@C84:an Improble, Egg-Shaped Endohedral Fullerene That Violates The Isolated Pentagon Rule [J]. J. Am. Chem. Soc,2006,128(35):11352-11353.(b) T. M. Zuo, K. Walker, M. M. Olmstead, et al. New Egg-Shaped Endohedral Fullerene:Non-Isolated Pentagon Structures of Tm3N@Cs (51365)-C84and Gd3N@Cs (51365)-C84[J]. Chem. Commun,2008,9:1067-1069.
[85]X. Lu, Y. F. Lian, C. M. Beavers, et al. Crystallographic X-ray Analyses of Yb@C2v (3)-C8o Reveal a Feasible Rule That Governs the Location of a Rare Earth Metal inside a Medium-Sized Fullerene[J]. J. Am. Chem. Soc.,2011,133(28):10772-10775.
[86]H. Shinohara, N. Hayashi, H. Sato, et al. Direct STM Imaging of Spherical Endohedral Discandium Fullerenes (Sc2@C84)[J]. J. Phys. Chem.,1993,97(51):13438-13440.
[87]X. Wang, T. Hashizume, H. Shinohara, et al. Scanning Tunneling Microscopy of C60on the Si (111)7x7Surface [J]. J. Appl. Phys.,1992,31(7B):L983-L986.
[88]B. Shi, X. Wang, H. Huang, et al. Scanning Tunneling Microscopy of Endohedral Metallofullerene Tb@C82on C60Film and Si (100)2x1Surface [J]. J. Phys. Chem. B,2001,105(46):11414-11418.
[89]A. Taninaka, K. Shino, T. Sugai, et al. Scanning Tunneling Microscopy Spectroscopy Studies of Lanthanum Endohedral Metallofullerenes [J]. Nano Lett.,2003,3:337-341.
[90]S. X. Zhao, J. Hao, B. Y. Sun, et al. Scanning Tunneling Microscopy Investigation of Substrate-Dependent Adsorption and Assembly of Metallofullerene Gd@C82on Cu (111) and Cu (100)[J]. J. Phys. Chem. C,2011,115(14):6265-6268.
[91]Y. Takano, S. Nagase, T. Akasaka, et al. Donor-Acceptor Conjugates of Lanthanum Endohedral Metallofullerene and π-Extended Tetrathiafulvalene [J]. J. Am. Chem. Soc.,2010,132(23):8048-8055.
[92]M. O.Ishitsuka, T. Akasaka, S. Nagase, et al. Regio selective Bis-functionalization of Endohedral Dimetallofullerene, La2@C8o:Extremal La-La Distance [J]. J. Am. Chem. Soc,2011,133(18):7128-7134.
[93]T.Yang, X.Zhao, S.Nagase, et al. Di-lanthanide Encapsulated into Large Fullerene Cioo:a DFT Surveyw [J]. Phys. Chem. Chem. Phys.,2011,13(11):5034-5037.
[94]J. Y. Wang, C. S.Lin, M. Y. Zhang, et al. Effect of Cage Size on the Third-Order Optical Properties of Endohedral Metallofullerenes Sc3N@C2n (2n=68,70,78, and80):A Theoretical Study [J]. International Journal of Quantum Chemistry,2012,112(3):759-769.
[95](a) F. F. Li, A. Rodriguez-Fortea, J. M. Poblet, et al. Reactivity of Metallic Nitride Endohedral Metallofullerene Anions:Electrochemical Synthesis of a Lu3N@Ih-C80Derivative [J]. J. Am. Chem. Soc.,2011,133(8):2760-2765.(b) B. Yang, R. F. Peng, B. Jin, et al. Preparation and Characterization of Langmuir-Blodgett Films of Endohedral Metallofullerene Gd@Cs2[J]. Synthetic Metals.,2011,161(9-10):770-774.
[96](a) X. Li, T. E. Yankeelov, G. D. Rosen, et al. Enhancement of Histological Volumes Through Averaging and Their Use for The Analysis of Magnetic Resonance Images [J]. Magnetic Resonance Imaging.,2009,27(3):401-416.(b) J. F. Zhang, P. P. Fatouros, C. Y. Shu, et al. High Relaxivity Trimetallic Nitride (Gd3N) Metallo-fullerene MRI Contrast Agents with Optimized Functionality [J]. Bioconjugate Chem.,2010,21(4):610-615.
[97](a)王晨.钇内嵌金属富勒烯制备与分离[D].硕士论文,黑龙江大学,2010.(b)王冲.Yb金属富勒烯包合物及特殊结构富勒烯的研究[D].硕士论文,大连理工大学,2007.(c)陈传宝.含金属钛的新型内嵌富勒烯的合成,分离及性质研究[D].博士论文,中国科学技术大学,2011.
[98]S. F. Yang, L. Z. Fan, S. H. Yang. Significantly Enhanced Photocurrent Efficiency of a Poly (3-hexylthiophene) Photoelectrochemical Device by Doping with The Endohedral Metallofullerene Dy@C82[J]. Chem. Phys. Lett.,2004,388(4-6):253-258.
[99]J. Tang, G. M. Xing, Y. L. Zhao. Switchable Semiconductive Property of the Polyhydroxylated Metallofullerene [J]. J. Phys. Chem. B,2007,111(41):11929-11934.
[100]J. R. Pinzon, C. M. Cardona, M. A. Herranz. Metal Nitride Cluster Fullerene M3N@C80(M=Y, Sc) Based Dyads:Synthesis, and Electrochemical, Theoretical and Photophysical Studies [J]. Chem. Eur. J.,2009,15(4):864-877.
[101]M. Yamada, N. Mizorogi, T. Tsuchiya, et al. Synthesis and Characterization of the D5h Isomer of the Endohedral Dimetallofullerene Ce2@C80:Two-Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage [J]. Chem. Eur. J.,2009,15(37):9486-9493.
[102]D. M Guldi, L. Feng, S. G. Radhakrishnan, et al. A Molecular Ce2@Ih-C80Switchs Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity [J]. J. Am. Chem. Soc,2010,132(26):9078-9086.