Endohedrals

Carbon Nanotubes and Related Structures: Synthesis, Characterization, Functionalization, and Applications

Volumn , Issue , 2010, Pages 455-490

  Feng, Lai ^a   Akasaka, Takeshi ^a   Nagase, Shigeru ^b  

^a UNIVERSITY OF TSUKUBA   (Japan)

^b INSTITUTE FOR MOLECULAR SCIENCE   (Japan)

Author keywords

Endohedral; Fullerene cage; Hybrid molecules; Metal cluster; Metallofullerene

Indexed keywords

EID: 80054901701     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9783527629930.ch15     Document Type: Chapter

References (144)

1. Heath, J.R., Zhang, Q., Liu, Y., Curl, R.F., Tittel, F.K., and Smalley, R.E. (1985) Lanthanum complexes of spheroidal carbon shells. J. Am. Chem. Soc., 107, 7779-7780.
2. Guo, T., Chai, Y., Jin, C., Haufler, R.E., Felipe Chibante, L.P., Fure, J., Michael Alford, J., Wang, L., and Smalley, R.E. (1991) Fullerenes with metals inside. J. Phys. Chem., 95, 7564-7568.
3. Akasaka, T. and Nagase, S. (eds) (2002) Endofullerenes: A New Family of Carbon Clusters, Kluwer Academic Publishers, Dordrecht. 4 Shinohara, H. (2000) Endohedral metallofullerenes. Rep. Prog. Phys., 63, 843-892.
4. Pietzak, B., Waiblinger, M., Murphy, T.A., Weidinger, A., Hohne, M., Dietel, E., and Hirsch, A. (1998) Properties of endohedralN@C60. Carbon, 36, 613-615.
5. Larsson, J.A., Greer, J.C., Harneit, W., and Weidinger, A. (2002) Phosphorous trapped within buckminsterfullerene. J. Chem. Phys., 116, 7849-7854.
6. Scheloske, M., Naydenov, B., Meyer, C., and Harneit, W. (2006) Synthesis and functionalization of fullerenes encapsulating atomic phosphorus. Isra. J. Chem., 46, 407-412.
7. Shabtai, E., Weitz, A., Haddon, R.C., Hoffman, R.E., Rabinovitz, M., Khong, A., Cross, R.J., Saunders, M., Cheng, P.C., and Scott, L.T. (1998) 3He NMR of He@C60 6"and He@C70 6". New records for the most shielded and the most deshielded 3He inside a fullerene. J. Am. Chem. Soc., 6389-6393.
8. Komatsu, K., Murata, M., and Murata, Y. (2005) Encapsulation of molecular hydrogen in fullerene C60 by organic synthesis. Science, 307, 238-240.
9. Murata, M., Murata, Y., and Komatsu, K. (2006) Synthesis and properties of endohedral C60 encapsulating molecular hydrogen. J. Am. Chem. Soc., 128, 8024-8033.
10. Takata, M., Umeda, B., Nishibori, E., Sakata, M., Saito, Y., Ohno, M., and Shinohara, H. (1995) Confirmation by X-ray-diffraction of the endohedral nature of the metallofullerene Y@C82. Nature, 377, 46-49.
11. Kato, H., Taninaka, A., Sugai, T., and Shinohara, H. (2003) Structure of a missing-caged metallofullerene: La2@C72. J. Am. Chem. Soc., 125, 7782-7783.
12. Wang, C.R., Kai, T., Tomiyama, T., Yoshida, T., Kobayashi, Y., Nishibori, E., Takata, M., Sakata, M., and Shinohara, H. (2000) Materials science - C66 fullerene encaging a scandium dimer. Nature, 408, 426-427.
13. Olmstead, M.M., Lee, H.M., Duchamp, J.C., Stevenson, S., Marciu, D., Dorn, H.C., and Balch, A.L. (2003) Sc3N@C68: folded pentalene coordination in an endohedral fullerene that does not obey the isolated pentagon rule. Angew. Chem. Int. Ed., 42, 900-903.
14. Beavers, C.M., Zuo, T.M., Duchamp, J.C., Harich, K., Dorn, H.C., Olmstead, M.M., and Balch, A.L. (2006) Tb3N@C84: an improbable, egg-shaped endohedral fullerene that violates the isolated pentagon rule. J. Am. Chem. Soc., 128, 11352-11353.
15. Stevenson, S., Rice, G., Glass, T., Harich, K., Cromer, F., Jordan, M.R., Craft, J., Hadju, E., Bible, R., Olmstead, M.M., Maitra, K., Fisher, A.J., Balch, A.L., and Dorn, H.C. (1999) Small-bandgap endohedral metallofullerenes in high yield and purity. Nature, 401, 55-57.
16. Yang, S.F. and Dunsch, L. (2005) A large family of dysprosium-based trimetallic nitride endohedral fullerenes: Dy3N@C2n (39(n(44). J. Phys. Chem. B, 109, 12320-12328.
17. Dunsch, L. and Yang, S. (2007) Metal nitride cluster fullerenes: their current state and future prospects. Small, 3, 1298-1320.
18. Yang, S.F. and Dunsch, L. (2006) Expanding the number of stable isomeric structures of theC80 cage: a new fullerene DY3N@C80. Chem. Eur. J., 12, 413-419.
19. Yang, S.F., Kalbac, M., Popov, A., and Dunsch, L. (2006) Gadolinium-based mixed metal nitride clusterfullerenes GdxSC3xN@C80 (x1/41, 2). ChemPhysChem, 7, 1990-1995.
20. Stevenson, S., Mackey, M.A., Stuart, M.A., Phillips, J.P., Easterling, M.L., Chancellor, C.J., Olmstead, M.M., and Balch, A.L. (2008) A distorted tetrahedral metal oxide cluster inside an icosahedral carbon cage. Synthesis, isolation, and structural characterization of Sc4(m3-O)2@Ih-C80. J. Am. Chem. Soc., 130, 11844-11845.
21. Lian, Y.F., Yang, S.F., and Yang, S.H. (2002) Revisiting the preparation of La@C82 (I and II) and La2@C80: efficient production of the "Minor" isomerLa@C82 (II). J. Phys. Chem. B, 106, 3112-3117.
22. Shi, Z.J., Okazaki, T., Shimada, T., Sugai, T., Suenaga, K., and Shinohara, H. (2003) Selective high-yield catalytic synthesis of terbium metallofullerenes and singlewall carbon nanotubes. J. Phys. Chem. B, 107, 2485-2489.
23. Stevenson, S., Mackey, M.A., Thompson, M.C., Coumbe, H.L., Madasu, P.K., Coumbe, C.E., and Phillips, J.P. (2007) Effect of copper metal on the yield of Sc3N@C80 metallofullerenes. Chem. Commun., 4263-4265.
24. Olmstead, M.M., de Bettencourt-Dias, A., Duchamp, J.C., Stevenson, S., Dorn, H.C., and Balch, A.L. (2000) Isolation and crystallographic characterization of ErSc2N@C80: an endohedral fullerene which crystallizes with remarkable internal order. J. Am. Chem. Soc., 122, 12220-12226.
25. Olmstead, M.H., de Bettencourt-Dias, A., Duchamp, J.C., Stevenson, S., Marciu, D., Dorn, H.C., and Balch, A.L. (2001) Isolation and structural characterization of the endohedral fullerene Sc3N@C78. Angew. Chem. Int. Ed., 40, 1223-1225.
26. Wolf, M., Muller, K.H., Skourski, Y., Eckert, D., Georgi, P., Krause, M., and Dunsch, L. (2005) Magnetic moments of the endohedral cluster fullerenes Ho3N@C80 and Tb3N@C80: the role of ligand fields. Angew. Chem. Int. Ed., 44, 3306-3309.
27. Zuo, T.M., Beavers, C.M., Duchamp, J.C., Campbell, A., Dorn, H.C., Olmstead, M.M., and Balch, A.L. (2007) Isolation and structural characterization of a family of endohedral fullerenes including the large, chiral cage fullerenes Tb3N@C88 and Tb3N@C86 as well as the Ih and D5h isomers of Tb3N@C80. J. Am. Chem. Soc., 129, 2035-2043.
28. Stevenson, S., Thompson, M.C., Coumbe, H.L., Mackey, M.A., Coumbe, C.E., and Phillips, J.P. (2007) Chemically adjusting plasma temperature, energy, and reactivity (CAPTEAR) method using NOx and combustion for selective synthesis of SC3N@C80 metallic nitride fullerenes. J. Am. Chem. Soc., 129, 16257-16262.
29. Tsuchiya, T., Wakahara, T., Shirakura, S., Maeda, Y., Akasaka, T., Kobayashi, K., Nagase, S., Kato, T., and Kadish, K.M. (2004) Reduction of endohedral metallofullerenes: a convenient method for isolation. Chem. Mater., 16, 4343-4346.
30. Ge, Z.X., Duchamp, J.C., Cai, T., Gibson, H.W., and Dorn, H.C. (2005) Purification of endohedral trimetallic nitride fullerenes in a single, facile step. J. Am. Chem. Soc., 127, 16292-16298.
31. Stevenson, S., Harich, K., Yu, H., Stephen, R.R., Heaps, D., Coumbe, C., and Phillips, J.P. (2006) Nonchromatographic "stir and filter approach"(SAFA) for isolating Sc3N@C80 metallofullerenes. J. Am. Chem. Soc., 128, 8829-8835.
32. Elliott, B., Yu, L., and Echegoyen, L. (2005) A simple isomeric separation of D5h and Ih Sc3N@C80 by selective chemical oxidation. J. Am. Chem. Soc., 127, 10885-10888.
33. Tsuchiya, T., Sato, K., Kurihara, H., Wakahara, T., Nakahodo, T., Maeda, Y., Akasaka, T., Ohkubo, K., Fukuzumi, S., Kato, T., Mizorogi, N., Kobayashi, K., and Nagase, S. (2006) Host-guest complexation of endohedral metallofullerene with azacrown ether and its application. J. Am. Chem. Soc., 128, 6699-6703.
34. Tsuchiya, T., Wakahara, T., Lian, Y.F., Maeda, Y., Akasaka, T., Kato, T., Mizorogi, N., and Nagase, S. (2006) Selective extraction and purification of endohedral metallofullerene from carbon soot. J. Phys. Chem. B, 110, 22517-22520.
35. Akasaka, T., Wakahara, T., Nagase, S., Kobayashi, K., Waelchli, M., Yamamoto, K., Kondo, M., Shirakura, S., Okubo, S., Maeda, Y., Kato, T., Kako, M., Nakadaira, Y., Nagahata, R., Gao, X., Van Caemelbecke, E., and Kadish, K.M. (2000) La@C82 anion. An unusually stable metallofullerene. J. Am. Chem. Soc., 122, 9316-9317.
36. Feng, L., Wakahara, T., Tsuchiya, T., Maeda, Y., Lian, Y.F., Akasaka, T., Mizorogi, N., Kobayashi, K., Nagase, S., and Kadish, K.M. (2005) Structural characterization of Y@C82. Chem. Phys. Lett., 405, 274-277.
37. Wakahara, T., Kobayashi, J., Yamada, M., Maeda, Y., Tsuchiya, T., Okamura, M., Akasaka, T., Waelchli, M., Kobayashi, K., Nagase, S., Kato, T., Kako, M., Yamamoto, K., and Kadish, K.M. (2004) Characterization of Ce@C82 and its anion. J. Am. Chem. Soc., 126, 4883-4887.
38. Akasaka, T., Wakahara, T., Nagase, S., Kobayashi, K., Waelchli, M., Yamamoto, K., Kondo, M., Shirakura, S., Maeda, Y., Kato, T., Kako, M., Nakadaira, Y., Gao, X., Van Caemelbecke, E., and Kadish, K.M. (2001) Structural determination of the La@C82 isomer. J. Phys. Chem. B, 105, 2971-2974.
39. Maeda, Y., Matsunaga, Y., Wakahara, T., Takahashi, S., Tsuchiya, T., Ishitsuka, M.O., Hasegawa, T., Akasaka, T., Liu, M.T.H., Kokura, K., Horn, E., Yoza, K., Kato, T., Okubo, S., Kobayashi, K., Nagase, S., and Yamamoto, K. (2004) Isolation and characterization of a carbene derivative of La@C82. J. Am. Chem. Soc., 126, 6858-6859.
40. Akasaka, T., Kono, T., Takematsu, Y., Nikawa, H., Nakahodo, T., Wakahara, T., Ishitsuka, M.O., Tsuchiya, T., Maeda, Y., Liu, M.T.H., Yoza, K., Kato, T., Yamamoto, K., Mizorogi, N., Slanina, Z., and Nagase, S. (2008) Does Gd@C82 have an anomalous endohedral structure? Synthesis and single crystal X-ray structure of the carbene adduct. J. Am. Chem. Soc., 130, 12840-12841.
41. Unpublished result.
42. Mizorogi, N. and Nagase, S. (2006) Do Eu@C82 and Gd@C82 have an anomalous endohedral structure? Chem. Phys. Lett., 431, 110-112.
43. Nishibori, E., Iwata, K., Sakata, M., Takata, M., Tanaka, H., Kato, H., and Shinohara, H. (2004) Anomalous endohedral structure of Gd@C82 metallofullerenes. Phys. Rev. B, 69, 113412.
44. Sun, B.Y., Sugai, T., Nishibori, E., Iwata, K., Sakata, M., Takata, M., and Shinohara, H. (2005) An anomalous endohedral structure of Eu@C82 metallofullerenes. Angew. Chem. Int. Ed., 44, 4568-4571.
45. Wakahara, T., Nikawa, H., Kikuchi, T., Nakahodo, T., Rahman, G.M.A., Tsuchiya, T., Maeda, Y., Akasaka, T., Yoza, K., Horn, E., Yamamoto, K., Mizorogi, N., Slanina, Z., and Nagase, S. (2006) La@C72 having a non-IPR carbon cage. J. Am. Chem. Soc., 128, 14228-14229.
46. Nikawa, H., Kikuchi, T., Wakahara, T., Nakahodo, T., Tsuchiya, T., Rahman, G.M.A., Akasaka, T., Maeda, Y., Yoza, K., Horn, E., Yamamoto, K., Mizorogi, N., and Nagase, S. (2005) Missing metallofullerene La@C74. J. Am. Chem. Soc., 127, 9684-9685.
47. 6. Acta Crystallogr., Sect. B, 60, 520-527.
48. Reich, A., Panthofer, M., Modrow, H., Wedig, U., and Jansen, M. (2004) The structure of Ba@C74. J. Am. Chem. Soc., 126, 14428-14434.
49. Tang, C.M., Fu, S.Y., Deng, K.M., Yuan, Y.B., Tan, W.S., Huang, D.C., and Wang, X. (2008) The density functional calculations on the structural stability, electronic properties, and static linear polarizability of the endohedral metallofullerene Ba@C74. J. Mol. Struct. (Theochem), 867, 111-115.
50. Tang, C.M., Deng, K.M., Tan, W.S., Yuan, Y.B., Liu, Y.Z., Wu, H.P., Huang, D.C., Hu, F.L., Yang, J.L., and Wang, X. (2007) Influence of a dichlorophenyl group on the geometric structure, electronic properties, and static linear polarizability of La@C74. Phys. Rev. A, 76, 013201.
51. Cao, B.P., Wakahara, T., Tsuchiya, T., Kondo, M., Maeda, Y., Rahman, G.M.A., Akasaka, T., Kobayashi, K., Nagase, S., and Yamamoto, K. (2004) Isolation, characterization, and theoretical study of La2@C78. J. Am. Chem. Soc., 126, 9164-9165.
52. Yang, S.F. and Dunsch, L. (2006) Di-and tridysprosium endohedral metallofullerenes with cages from C94 to C100. Angew. Chem. Int. Ed., 45, 1299-1302.
53. Cao, B.P., Hasegawa, M., Okada, K., Tomiyama, T., Okazaki, T., Suenaga, K., and Shinohara, H. (2001) EELS and 13C NMR characterization of pure Ti2@C80 metallofullerene. J. Am. Chem. Soc., 123, 9679-9680.
54. Cao, B.P., Suenaga, K., Okazaki, T., and Shinohara, H. (2002) Production, isolation, and EELS characterization of Ti2@C84 dititanium metallofullerenes. J. Phys. Chem. B, 106, 9295-9298.
55. Tagmatarchis, N. and Shinohara, H. (2000) Production, separation, isolation, and spectroscopic study of dysprosium endohedral metallofullerenes. Chem. Mater., 12, 3222-3226.
56. Yamada, M., Wakahara, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Mizorogi, N., and Nagase, S. (2008) Spectroscopic and theoretical study of endohedral dimetallofullerene having a Non-IPR fullerene cage: Ce2@C72. J. Phys. Chem. A, 112, 7627-7631.
57. Lu, X., Nikawa, H., Nakahodo, T., Tsuchiya, T., Ishitsuka, M.O., Maeda, Y., Akasaka, T., Toki, M., Sawa, H., Slanina, Z., Mizorogi, N., and Nagase, S. (2008) Chemical understanding of a non-IPR metallofullerene: stabilization of encaged metals on fused-pentagon bonds in La2@C72. J. Am. Chem. Soc., 130, 9129-9136.
58. Yamada, M., Someya, C., Wakahara, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Yoza, K., Horn, E., Liu, M.T.H., Mizorogi, N., and Nagase, S. (2008) Metal atoms collinear with the spiro carbon of 6,6- open adducts, M2@C80(Ad) (M1/4La and Ce, Ad1/4adamantylidene). J. Am. Chem. Soc., 130, 1171-1176.
59. Cao, B., Nikawa, H., Nakahodo, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Sawa, H., Slanina, Z., Mizorogi, N., and Nagase, S. (2008) Addition of adamantylidene to La2@C78: isolation and single-crystal X-ray structural determination of the monoadducts. J. Am. Chem. Soc., 130, 983-989.
60. Olmstead, M.M., de Bettencourt-Dias, A., Stevenson, S., Dorn, H.C., and Balch, A.L. (2002) Crystallographic characterization of the structure of the endohedral fullerene {Er2 @ C82 Isomer I} with Cs cage symmetry and multiple sites for erbium along a band of ten contiguous hexagons. J. Am. Chem. Soc., 124, 4172-4173.
61. Olmstead, M.M., Lee, H.M., Stevenson, S., Dorn, H.C., and Balch, A.L. (2002) Crystallographic characterization of Isomer 2 of Er2@C82 and comparison with Isomer 1 of Er2@C82. Chem. Commun., 2688-2689.
62. Zuo, T.M., Xu, L.S., Beavers, C.M., Olmstead, M.M., Fu, W.J., Crawford, D., Balch, A.L., and Dorn, H.C. (2008) M2@C79N (M1/4Y, Tb): isolation and characterization of stable endohedral metallofullerenes exhibiting M-M bonding interactions inside aza[80]fullerene cages. J. Am. Chem. Soc., 130, 12992-12997.
63. Wang, C.R., Kai, T., Tomiyama, T., Yoshida, T., Kobayashi, Y., Nishibori, E., Takata, M., Sakata, M., and Shinohara, H. (2001) A scandium carbide endohedral metallofullerene: (Sc2C2)@C84. Angew. Chem. Int. Ed., 40, 397-399.
64. Iiduka, Y., Wakahara, T., Nakajima, K., Nakahodo, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Yoza, K., Liu, M.T.H., Mizorogi, N., and Nagase, S. (2007) Experimental and theoretical studies of the scandium carbide endohedral metallofullerene Sc2C2@C82 and its carbene derivative. Angew. Chem. Int. Ed., 46, 5562-5564.
65. Iiduka, Y., Wakahara, T., Nakajima, K., Tsuchiya, T., Nakahodo, T., Maeda, Y., Akasaka, T., Mizorogi, N., and Nagase, S. (2006) 13C NMR spectroscopic study of scandium dimetallofullerene, Sc2@C84 versus (Sc2C2)@ C82. Chem. Commun., 2057-2059.
66. Yamazaki, Y., Nakajima, K., Wakahara, T., Tsuchiya, T., Ishitsuka, M.O., Maeda, Y., Akasaka, T., Waelchli, M., Mizorogi, N., and Nagase, S. (2008) Observation of 13C NMR chemical shifts of metal carbides encapsulated in fullerenes: Sc2C2@C82, Sc2C2@C84, and Sc3C2@C80. Angew. Chem. Int. Ed., 47, 7905-7908.
67. Nishibori, E., Ishihara, M., Takata, M., Sakata, M., Ito, Y., Inoue, T., and Shinohara, H. (2006) Bent (metal)2C2 clusters encapsulated in (Sc2C2) @C82(III) and (Y2C2)@C82(III) metallofullerenes. Chem. Phys. Lett., 433, 120-124.
68. Nishibori, E., Narioka, S., Takata, M., Sakata, M., Inoue, T., and Shinohara, H. (2006) A C2 molecule entrapped in the pentagonal-dodecahedral Y2 cage in Y2C2@C82(III). ChemPhysChem, 7, 345-348.
69. Iiduka, Y., Wakahara, T., Nakahodo, T., Tsuchiya, T., Sakuraba, A., Maeda, Y., Akasaka, T., Yoza, K., Horn, E., Kato, T., Liu, M.T.H., Mizorogi, N., Kobayashi, K., and Nagase, S. (2005) Structural determination of metallofuIlerene SC3C82 revisited: a surprising finding. J. Am. Chem. Soc., 127, 12500-12501.
70. Nishibori, E., Terauchi, I., Sakata, M., Takata, M., Ito, Y., Sugai, T., and Shinohara, H. (2006) High-resolution analysis of (Sc3C2)@C80 metallofullerene by third generation synchrotron radiation X-ray powder diffraction. J. Phys. Chem. B, 110, 19215-19219.
71. Shi, Z.Q., Wu, X., Wang, C.R., Lu, X., and Shinohara, H. (2006) Isolation and characterization of Sc2C2@C68: a metalcarbide endofullerene with a non-IPR carbon cage. Angew. Chem. Int. Ed., 45, 2107-2111.
72. Takata, M., Nishibori, E., Sakata, M., Inakuma, M., Yamamoto, E., and Shinohara, H. (1999) Triangle scandium cluster imprisoned in a fullerene cage. Phys. Rev. Lett., 83, 2214-2217.
73. Valencia, R., Rodriguez-Fortea, A., and Poblet, J.M. (2008) Understanding the stabilization of metal carbide endohedral fullerenes M2C2@C82 and related systems. J. Phys. Chem. A, 112, 4550-4555.
74. Wang, X.L., Zuo, T.M., Olmstead, M.M., Duchamp, J.C., Glass, T.E., Cromer, F., Balch, A.L., and Dorn, H.C. (2006) Preparation and structure of CeSc2N@C80: an icosahedral carbon cage enclosing an acentric CeSc2N unit with buried f electron spin. J. Am. Chem. Soc., 128, 8884-8889.
75. Stevenson, S., Chancellor, C.J., Lee, H.M., Olmstead, M.M., and Balch, A.L. (2008) Internal and external factors in the structural organization in cocrystals of the mixed-metal endohedrals (GdSc2N@Ih-C80, Gd2ScN@Ih-C80, and TbSc2N@Ih-C80) and nickel(II) octaethylporphyrin. Inorg. Chem., 47, 1420-1427.
76. Chen, N., Zhang, E.Y., and Wang, C.R. (2006) C-80 encaging four different atoms: the synthesis, isolation, and characterizations of ScYErN@C80. J. Phys. Chem. B, 110, 13322-13325.
77. Haddon, R.C. and Raghavachari, K. (eds) (1993) Chapter 7, in In Buckminsterfullerenes, VCH, New York.
78. 805(o-xylene). Chem. Eur. J., 8, 4528-4535.
79. Zuo, T.M., Olmstead, M.M., Beavers, C.M., Balch, A.L., Wang, G.B., Yee, G.T., Shu, C.Y., Xu, L.S., Elliott, B., Echegoyen, L., Duchamp, J.C., and Dorn, H.C. (2008) Preparation and structural characterization of the Ih and the D5h isomers of the endohedral fullerenes Tm3N@C80: icosahedral C80 cage encapsulation of a trimetallic nitride magnetic cluster with three uncoupled Tm3thorn ions. Inorg. Chem., 47, 5234-5244.
80. Echegoyen, L., Chancellor, C.J., Cardona, C.M., Elliott, B., Rivera, J., Olmstead, M.M., and Balch, A.L. (2006) X-Ray crystallographic and EPR spectroscopic characterization of a pyrrolidine adduct of Y3N@C80. Chem. Commun., 2653-2655.
81. Yang, S.F., Troyanov, S.I., Popov, A.A., Krause, M., and Dunsch, L. (2006) Deviation from the planarity - a large Dy3N cluster encapsulated in an Ih-C80 cage: an X-ray crystallographic and vibrational spectroscopic study. J. Am. Chem. Soc., 128, 16733-16739.
82. Stevenson, S., Phillips, J.P., Reid, J.E., Olmstead, M.M., Rath, S.P., and Balch, A.L. (2004) Pyramidalization of Gd3N inside a C80 cage. The synthesis and structure of Gd3N@C80. Chem. Commun., 2814-2815.
83. Greenwood, N.N. and Earnshaw, A. (1984) Chemistry of the Elements, Pergamon, Oxford, UK. 85 Mercado, B.Q., Beavers, C.M., Olmstead, M.M., Chaur, M.N., Walker, K., Holloway, B.C., Echegoyen, L., and Balch, A.L. (2008) Is the isolated pentagon rule merely a suggestion for endohedral fullerenes? The structure of a second egg-shaped endohedral fullerene-Gd3N@Cs(39663)-C82. J. Am. Chem. Soc., 130, 7854-7855.
84. Zuo, T., Walker, K., Olmstead, M.M., Melin, F., Holloway, B.C., Echegoyen, L., Dorn, H.C., Chaur, M.N., Chancellor, C.J., Beavers, C.M., Balch, A.L., and Athans, A.J. (2008) New egg-shaped fullerenes: non-isolated pentagon structures of Tm3N@Cs(51365)-C84 and Gd3N@Cs(51365)-C84. Chem. Commun., 1067-1069.
85. Popov, A.A. and Dunsch, L. (2007) Structure, stability, and cluster-cage interactions in nitride clusterfullerenes M3N@C2n (M1/4Sc, Y; 2n1/468-98): a density functional theory study. J. Am. Chem. Soc., 129, 11835-11849.
86. Yang, S., Popov, A.A., and Dunsch, L. (2008) Large mixed metal nitride clusters encapsulated in a small cage: the confinement of the C68-based clusterfullerenes. Chem. Commun., 2885-2887.
87. Slanina, Z., Chen, Z.F., Schleyer, P.V., Uhlik, F., Lu, X., and Nagase, S. (2006) La2@C72 and Sc2@C72: computational characterizations. J. Phys. Chem. A, 110, 2231-2234.
88. Iiduka, Y., Ikenaga, O., Sakuraba, A., Wakahara, T., Tsuchiya, T., Maeda, Y., Nakahodo, T., Akasaka, T., Kako, M., Mizorogi, N., and Nagase, S. (2005) Chemical reactivity of Sc3N@C80 and La2@C80. J. Am. Chem. Soc., 127, 9956-9957.
89. Cai, T., Xu, L.S., Anderson, M.R., Ge, Z.X., Zuo, T.M., Wang, X.L., Olmstead, M.M., Balch, A.L., Gibson, H.W., and Dorn, H.C. (2006) Structure and enhanced reactivity rates of the D5h Sc3N@C80 and Lu3N@C80 metallofullerene isomers: the importance of the pyracylene motif. J. Am. Chem. Soc., 128, 8581-8589.
90. Lide, D.R. (ed.) (2000) Handbook of Chemistry and Physics, 81st edn, CRC, Boca Raton, FL.
91. Xu, J.X., Li, M.X., Shi, Z.J., and Gu, Z.N. (2006) Electrochemical survey: the effect of the cage size and structure on the electronic structures of a series of ytterbium metallofullerenes. Chem. Eur. J., 12, 562-567.
92. Chaur, M.N., Melin, F., Elliott, B., Athans, A.J., Walker, K., Holloway, B.C., and Echegoyen, L. (2007) Gd3N@C2n (n1/440, 42, and 44): remarkably low HOMO-LUMO gap and unusual electrochemical reversibility of Gd3N@C88. J. Am. Chem. Soc., 129, 14826-14829.
93. Solodovnikov, S.P. and Lebedkin, S.F. (2003) ESR spectra of endohedral metallofullerene Ce@C82 radical anions in dimethylformamide and pyridine. Russ. Chem. B, 52, 1111-1113.
94. Tsuchiya, T., Kurihara, H., Sato, K., Wakahara, T., Akasaka, T., Shimizu, T., Kamigata, N., Mizorogi, N., and Nagase, S. (2006) Supramolecular complexes of La@C82 with unsaturated thiacrown ethers. Chem. Commun., 3585-3587.
95. Yang, S.F., Rapta, P., and Dunsch, L. (2007) The spin state of a charged non-IPR fullerene: the stable radical cation of Sc3N@C68. Chem. Commun., 189-191.
96. Iezzi, E.B., Duchamp, J.C., Harich, K., Glass, T.E., Lee, H.M., Olmstead, M.M., Balch, A.L., and Dorn, H.C. (2002) A symmetric derivative of the trimetallic nitride endohedral metallofullerene, Sc3N@C80. J. Am. Chem. Soc., 124, 524-525.
97. Lu, X., He, X.R., Feng, L., Shi, Z.J., and Gu, Z.N. (2004) Synthesis of pyrrolidine ring-fused metallofullerene derivatives. Tetrahedron, 60, 3713-3716.
98. Cao, B.P., Wakahara, T., Maeda, Y., Han, A.H., Akasaka, T., Kato, T., Kobayashi, K., and Nagase, S. (2004) Lanthanum endohedral metallofulleropyrrolidines: synthesis, isolation, and EPR characterization. Chem. Eur. J., 10, 716-720.
99. Feng, L., Lu, X., He, X.R., Shi, Z.J., and Gu, Z.N. (2004) Reactions of endohedral metallofullerenes with azomethine ylides: an efficient route toward metallofullerene-pyrrolidines. Inorg. Chem. Commun., 7, 1010-1013.
100. Cardona, C.M., Kitaygorodskiy, A., Ortiz, A., Herranz, M.A., and Echegoyen, L. (2005) The first fulleropyrrolidine derivative of Sc3N@C80: pronounced chemical shift differences of the geminal protons on the pyrrolidine ring. J. Org. Chem., 70, 5092-5097.
101. Cai, T., Ge, Z.X., Iezzi, E.B., Glass, T.E., Harich, K., Gibson, H.W., and Dorn, H.C. (2005) Synthesis and characterization of the first trimetallic nitride templated pyrrolidino endohedral metallofullerenes. Chem. Commun., 3594-3596.
102. Cardona, C.M., Kitaygorodskiy, A., and Echegoyen, L. (2005) Trimetallic nitride endohedral metallofullerenes: reactivity dictated by the encapsulated metal cluster. J. Am. Chem. Soc., 127, 10448-10453.
103. 80(x1/40-3). Org. Lett., 9, 2011-2013.
104. Cai, T., Slebodnick, C., Xu, L., Harich, K., Glass, T.E., Chancellor, C., Fettinger, J.C., Olmstead, M.M., Balch, A.L., Gibson, H.W., and Dorn, H.C. (2006) A pirouette on a metallofullerene sphere: interconversion of isomers of Ntritylpyrrolidino Ih Sc3N@C80. J. Am. Chem. Soc., 128, 6486-6492.
105. Yamada, M., Wakahara, T., Nakahodo, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Yoza, K., Horn, E., Mizorogi, N., and Nagase, S. (2006) Synthesis and structural characterization of endohedral pyrrolidinodimetallofullerene: La2@C80(CH2)2NTrt. J. Am. Chem. Soc., 128, 1402-1403.
106. Cai, T., Xu, L., Gibson, H.W., Dorn, H.C., Chancellor, C.J., Olmstead, M.M., and Balch, A.L. (2007) SC3N@C78: encapsulated cluster regiocontrol of adduct docking on an ellipsoidal metallofullerene sphere. J. Am. Chem. Soc., 129, 10795-10800.
107. Yamada, M., Wakahara, T., Tsuchiya, T., Maeda, Y., Kako, M., Akasaka, T., Yoza, K., Horn, E., Mizorogi, N., and Nagase, S. (2008) Location of the metal atoms in Ce2@C78 and its bis-silylated derivative. Chem. Commun., 558-560.
108. Lu, X., Nikawa, H., Tsuchiya, T., Maeda, Y., Ishitsuka, M.O., Akasaka, T., Toki, M., Sawa, H., Slanina, Z., Mizorogi, N., and Nagase, S. (2008) Bis-carbene adducts of non-IPR La2@C72: localization of high reactivity around fused pentagons and electrochemical properties. Angew. Chem. Int. Ed., 47, 8642-8645.
109. Yamada, M., Feng, L., Wakahara, T., Tsuchiya, T., Maeda, Y., Lian, Y.F., Kako, M., Akasaka, T., Kato, T., Kobayashi, K., and Nagase, S. (2005) Synthesis and characterization of exohedrally silylated M@C82 (M1/4Yand La). J. Phys. Chem. B, 109, 6049-6051.
110. Akasaka, T., Okubo, S., Kondo, M., Maeda, Y., Wakahara, T., Kato, T., Suzuki, T., Yamamoto, K., Kobayashi, K., and Nagase, S. (2000) Isolation and characterization of two Pr@C82 isomers. Chem. Phys. Lett., 319, 153-156.
111. Akasaka, T., Nagase, S., Kobayashi, K., Suzuki, T., Kato, T., Yamamoto, K., Funasaka, H., and Takahashi, T. (1995) Exohedral derivatization of an endohedral metallofullerene Gd@C82. J. Chem. Soc., Chem. Commun., 1343-1344.
112. Wakahara, T., Yamada, M., Takahashi, S., Nakahodo, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Kako, M., Yoza, K., Horn, E., Mizorogi, N., and Nagase, S. (2007) Twodimensional hopping motion of encapsulated La atoms in silylated La2@C80. Chem. Commun., 2680-2682.
113. Yamada, M., Nakahodo, T., Wakahara, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Kako, M., Yoza, K., Horn, E., Mizorogi, N., Kobayashi, K., and Nagase, S. (2005) Positional control of encapsulated atoms inside a fullerene cage by exohedral addition. J. Am. Chem. Soc., 127, 14570-14571.
114. Akasaka, T., Nagase, S., Kobayashi, K., Suzuki, T., Kato, T., Kikuchi, K., Achiba, Y., Yamamoto, K., Funasaka, H., and Takahashi, T. (1995) Synthesis of the first adducts of the dimetallofullerenes La2@C80 and SC2@C84 by addition of a disilirane. Angew. Chem. Int. Ed., 34, 2139-2141.
115. Wakahara, T., Iiduka, Y., Ikenaga, O., Nakahodo, T., Sakuraba, A., Tsuchiya, T., Maeda, Y., Kako, M., Akasaka, T., Yoza, K., Horn, E., Mizorogi, N., and Nagase, S. (2006) Characterization of the bissilylated endofullerene Sc3N@C80. J. Am. Chem. Soc., 128, 9919-9925.
116. Chuang, S.C., Santhosh, K.C., Lin, C.H., Wang, S.L., and Cheng, C.H. (1999) Synthesis and chemistry of fullerene derivatives bearing phosphorus substituents. Unusual reaction of phosphines with electron-deficient acetylenes and C60. J. Org. Chem., 64, 6664-6669.
117. Li, X.F., Fan, L.Z., Liu, D.F., Sung, H.H.Y., Williams, I.D., Yang, S., Tan, K., and Lu, X. (2007) Synthesis of a Dy@C82 derivative bearing a single phosphorus substituent via a zwitterion approach. J. Am. Chem. Soc., 129, 10636-10637.
118. Lukoyanova, O., Cardona, C.M., Rivera, J., Lugo-Morales, L.Z., Chancellor, C.J., Olmstead, M.M., Rodriguez-Fortea, A., Poblet, J.M., Balch, A.L., and Echegoyen, L. (2007) "Open rather than closed" malonate methano-fullerene derivatives. The formation of methanofulleroid adducts of Y3N@C80. J. Am. Chem. Soc., 129, 10423-10430.
119. Fatouros, P.P., Corwin, F.D., Chen, Z.J., Broaddus, W.C., Tatum, J.L., Kettenmann, B., Ge, Z., Gibson, H.W., Russ, J.L., Leonard, A.P., Duchamp, J.C., and Dorn, H.C. (2006) In vitro and in vivo imaging studies of a new endohedral metallofullerene nanoparticle. Radiology, 240, 756-764.
120. Cai, T., Xu, L., Shu, C., Champion, H.A., Reid, J.E., Anklin, C., Anderson, M.R., Gibson, H.W., and Dorn, H.C. (2008) Selective formation of a symmetric Sc3N@C78 bisadduct: adduct docking controlled by an internal trimetallic nitride cluster. J. Am. Chem. Soc., 130, 2136-2137.
121. Chaur, M.N., Melin, F., Athans, A.J., Elliott, B., Walker, K., Holloway, B.C., and Echegoyen, L. (2008) The influence of cage size on the reactivity of trimetallic nitride metallofullerenes: a mono- and bis-methanoadduct of Gd3N@C80 and a monoadduct of Gd3N@C84. Chem. Commun., 2665-2667.
122. Feng, L., Nakahodo, T., Wakahara, T., Tsuchiya, T., Maeda, Y., Akasaka, T., Kato, T., Horn, E., Yoza, K., Mizorogi, N., and Nagase, S. (2005) A singly bonded derivative of endohedral metallofullerene: La@C82CBr (COOC2H5)2. J. Am. Chem. Soc., 127, 17136-17137.
123. Feng, L., Wakahara, T., Nakahodo, T., Tsuchiya, T., Piao, Q., Maeda, Y., Lian, Y., Akasaka, T., Horn, E., Yoza, K., Kato, T., Mizorogi, N., and Nagase, S. (2006) The bingel monoadducts of La@C82: synthesis, characterization, and electrochemistry. Chem. Eur. J., 12, 5578-5586.
124. Feng, L., Tsuchiya, T., Wakahara, T., Nakahodo, T., Piao, Q., Maeda, Y., Akasaka, T., Kato, T., Yoza, K., Horn, E., Mizorogi, N., and Nagase, S. (2006) Synthesis and characterization of a bisadduct of La@C82. J. Am. Chem. Soc., 128, 5990-5991.
125. Shu, C.Y., Cai, T., Xu, L.S., Zuo, T.M., Reid, J., Harich, K., Dorn, H.C., and Gibson, H.W. (2007) Manganese(III)- catalyzed free radical reactions on trimetallic nitride endohedral metallofullerenes. J. Am. Chem. Soc., 129, 15710-15717.
126. Shustova, N.B., Popov, A.A., Mackey, M.A., Coumbe, C.E., Phillips, J.P., Stevenson, S., Strauss, S.H., and Boltalina, O.V. (2007) Radical trifluoromethylation of Sc3N@C80. J. Am. Chem. Soc., 129, 11676-11677.
127. Kareev, I.E., Lebedkin, S.F., Bubnov, V.P., Yagubskii, E.B., Ioffe, I.N., Khavrel, P.A., Kuvychko, I.V., Strauss, S.H., and Boltalina, O.V. (2005) Trifluoromethylated endohedral metallofullerenes: synthesis and characterization of Y@C82(CF3)5. Angew. Chem. Int. Ed., 44, 1846-1849.
128. Tumanskii, B.L. and Kalina, O.G. (eds) (2001) Endofullerenes: Radical Reaction of Fullerene Derivatives, Kluwer Academic Publishers, Dordrecht, The Netherlands.
129. Tagmatarchis, N., Taninaka, A., and Shinohara, H. (2002) Production and EPR characterization of exohedrally perfluoroalkylated paramagnetic lanthanum metallofullerenes: (La@C82)-(C8F17)2. Chem. Phys. Lett., 355, 226-232.
130. Takano, Y., Yomogida, A., Nikawa, H., Yamada, M., Wakahara, T., Tsuchiya, T., Ishitsuka, M.O., Maeda, Y., Akasaka, T., Kato, T., Slanina, Z., Mizorogi, N., and Nagase, S. (2008) Radical coupling reaction of paramagnetic endohedral metallofullerene La@C82. J. Am. Chem. Soc., 130, 16224-16230.
131. Mikawa, M., Kato, H., Okumura, M., Narazaki, M., Kanazawa, Y., Miwa, N., and Shinohara, H. (2001) Paramagnetic water-soluble metallofullerenes having the highest relaxivity for MRI contrast agents. Bioconjug. Chem., 12, 510-514.
132. Bolskar, R.D., Benedetto, A.F., Husebo, L.O., Price, R.E., Jackson, E.F., Wallace, S., Wilson, L.J., and Alford, J.M. (2003) First soluble M@C60 derivatives provide enhanced access to metallofullerenes and permit in vivo evaluation of Gd@C60[C (COOH)2]10 as a MRI contrast agent. J. Am. Chem. Soc., 125, 5471-5478.
133. Shu, C.Y., Zhang, E.Y., Xiang, J.F., Zhu, C.F., Wang, C.R., Pei, X.L., and Han, H.B. (2006) Aggregation studies of the watersoluble gadofullerene magnetic resonance imaging contrast agent: [Gd@C82O6(OH)16(NHCH2 CH2COOH)8]x. J. Phys. Chem. B, 110, 15597-15601.
134. MacFarland, D.K., Walker, K.L., Lenk, R.P., Wilson, S.R., Kumar, K., Kepley, C.L., and Garbow, J.R. (2008) Hydrochalarones: a novel endohedral metallofullerene platform for enhancing magnetic resonance imaging contrast. J. Med. Chem., 51, 3681-3683.
135. Toth, E., Bolskar, R.D., Borel, A., Gonzalez, G., Helm, L., Merbach, A.E., Sitharaman, B., and Wilson, L.J. (2005) Water-soluble gadofullerenes: toward high-relaxivity, pH-responsive MRI contrast agents. J. Am. Chem. Soc., 127, 799-805.
136. Laus, S., Sitharaman, B., Toth, V., Bolskar, R.D., Helm, L., Asokan, S., Wong, M.S., Wilson, L.J., and Merbach, A.E. (2005) Destroying gadofullerene aggregates by salt addition in aqueous solution of Gd@C60(OH)x and Gd@C60[C (COOH)2]10. J. Am. Chem. Soc., 127, 9368-9369.
137. Okazaki, T., Shimada, T., Suenaga, K., Ohno, Y., Mizutani, T., Lee, J., Kuk, Y., and Shinohara, H. (2003) Electronic properties of Gd@C82 metallofullerene peapods: (Gd @ C82)n@SWNTs. Appl. Phys. A, 76, 475-478.
138. Hirahara, K., Suenaga, K., Bandow, S., Kato, H., Okazaki, T., Shinohara, H., and Iijima, S. (2000) One-dimensional metallofullerene crystal generated inside single-walled carbon nanotubes. Phys. Rev. Lett., 85, 5384-5387.
139. Chiu, P.W., Gu, G., Kim, G.T., Philipp, G., Roth, S., Yang, S.F., and Yang, S. (2001) Temperature-induced change from p to n conduction in metallofullerene nanotube peapods. Appl. Phys. Lett., 79, 3845-3847.
140. Debarre, A., Jaffiol, R., Julien, C., Nutarelli, D., Richard, A., and Tchenio, P. (2003) Specific Raman signatures of a dimetallofullerene peapod. Phys. Rev. Lett., 91, 085501-085504.
141. Debarre, A., Jaffiol, R., Julien, C., Richard, A., Nutarelli, D., and Tchenio, P. (2003) Antenna effect in dimetallofullerene peapods. Chem. Phys. Lett., 380, 6-11.
142. Kalbac, M., Kavan, L., Zukalova, M., Yang, S.F., Cech, J., Roth, S., and Dunsch, L. (2007) The change of the state of an endohedral fullerene by encapsulation into SWCNT: a Raman spectroelectrochemical study of Dy3N@C80 peapods. Chem. Eur. J., 13, 8811-8817.
143. Tsuchiya, T., Kumashiro, R., Tanigaki, K., Matsunaga, Y., Ishitsuka, M.O., Wakahara, T., Maeda, Y., Takano, Y., Aoyagi, M., Akasaka, T., Liu, M.T.H., Kato, T., Suenaga, K., Jeong, J.S., Iijima, S., Kimura, F., Kimura, T., and Nagase, S. (2008) Nanorods of endohedral metallofullerene derivative. J. Am. Chem. Soc., 130, 450.
144. Pinzon, J.R., Cardona, C.M., Athans, A.J., Gayathri, S.S., Guldi, D.M., Herranz, M.A., Martin, N., Torres, T., and Echegoyen, L. (2007) Sc3N@C80-ferrocene electron-donor/acceptor conjugates as promising materials for photovoltaic applications. J. Am. Chem. Soc., 120, 4241-4244.