Current status and future developments of endohedral metallofullerenes.

Endohedral metallofullerenes (EMFs), a new class of hybrid molecules formed by encapsulation of metallic species inside fullerene cages, exhibit unique properties that differ distinctly from those of empty fullerenes because of the presence of metals and their hybridization effects via electron transfer. This critical review provides a balanced but not an exhaustive summary regarding almost all aspects of EMFs, including the history, the classification, current progress in the synthesis, extraction, isolation, and characterization of EMFs, as well as their physiochemical properties and applications in fields such as electronics, photovoltaics, biomedicine, and materials science. Emphasis is assigned to experimentally obtained results, especially the X-ray crystallographic characterizations of EMFs and their derivatives, rather than theoretical calculations, although the latter has indeed enhanced our knowledge of metal-cage interactions. Finally, perspectives related to future developments and challenges in the research of EMFs are proposed. (381 references).

[1]  A. Rodríguez‐Fortea,et al.  Large fullerenes stabilized by encapsulation of metallic clusters. , 2007, Chemical communications.

[2]  R. Dorsinville,et al.  Dispersion and pulse-duration dependence of the nonlinear optical response of Gd2 at C80 , 2001 .

[3]  Xing Lu,et al.  Bis-carbene adducts of non-IPR La2@C72: localization of high reactivity around fused pentagons and electrochemical properties. , 2008, Angewandte Chemie.

[4]  B. Sitharaman,et al.  Water-soluble gadofullerenes: toward high-relaxivity, pH-responsive MRI contrast agents. , 2005, Journal of the American Chemical Society.

[5]  Steven Stevenson,et al.  Sc2(mu2-O) trapped in a fullerene cage: the isolation and structural characterization of Sc2(mu2-O)@C(s)6-C82 and the relevance of the thermal and entropic effects in fullerene isomer selection. , 2010, Journal of the American Chemical Society.

[6]  Hideyuki Funasaka,et al.  13C and 139La NMR Studies of La2@C80: First Evidence for Circular Motion of Metal Atoms in Endohedral Dimetallofullerenes , 1997 .

[7]  Lukas Novotny,et al.  Plasmon-Enhanced Photoemission from a Single Y3N@C80 Fullerene† , 2010 .

[8]  Z. Gu,et al.  Synthesis of pyrrolidine ring-fused metallofullerene derivatives , 2004 .

[9]  J. Alford,et al.  Isolation and properties of small-bandgap fullerenes , 1998, Nature.

[10]  R. Kaner,et al.  Lanthanum carbide (La2C80): a soluble dimetallofullerene , 1991 .

[11]  D. Guldi,et al.  Synthesis and charge-transfer chemistry of La2@I(h)-C80/Sc3N@I(h)-C80-zinc porphyrin conjugates: impact of endohedral cluster. , 2011, Journal of the American Chemical Society.

[12]  K. Ohkubo,et al.  Host-guest complexation of endohedral metallofullerene with azacrown ether and its application. , 2006, Journal of the American Chemical Society.

[13]  S. Nagase,et al.  Endohedrally Metal-Doped Heterofullerenes: La@C81N and La2@C79N , 1999 .

[14]  N. Cue,et al.  Isolation and characterization of a new metallofullerene Nd@C82 , 1996 .

[15]  D. Guldi,et al.  Enhanced binding strengths of acyclic porphyrin hosts with endohedral metallofullerenes , 2011 .

[16]  S. Nagase,et al.  Characterization of the bis-silylated endofullerene Sc3N@C80. , 2006, Journal of the American Chemical Society.

[17]  R. Price,et al.  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. , 2003, Journal of the American Chemical Society.

[18]  D. Guldi,et al.  Sc3N@C80-ferrocene electron-donor/acceptor conjugates as promising materials for photovoltaic applications. , 2008, Angewandte Chemie.

[19]  Xing Lu,et al.  Current progress on the chemical functionalization and supramolecular chemistry of M@C82. , 2011, Nanoscale.

[20]  S. Iijima,et al.  Fine-structure analysis of Gd M 45 near-edge EELS on the valence state of Gd\@C 82 microcrystals , 2000 .

[21]  L. Echegoyen,et al.  New M(3)N@C(2n) endohedral metallofullerene families (M=Nd, Pr, Ce; n=40-53): expanding the preferential templating of the C(88) cage and approaching the C(96) cage. , 2008, Chemistry.

[22]  M. Sakata,et al.  Anomalous endohedral structure of Gd@C 82 metallofullerenes , 2004 .

[23]  P. Fatouros,et al.  Conjugation of a water-soluble gadolinium endohedral fulleride with an antibody as a magnetic resonance imaging contrast agent. , 2008, Bioconjugate chemistry.

[24]  Kai Tan,et al.  Russian-doll-type metal carbide endofullerene: synthesis, isolation, and characterization of Sc4C2@C80. , 2009, Journal of the American Chemical Society.

[25]  Mingzhi Jiao,et al.  Synthesis, isolation, and addition patterns of trifluoromethylated D5h and I(h) isomers of Sc3N@C80: Sc3N@D5h-C80(CF3)18 and Sc3N@I(h)-C80(CF3)14. , 2011, Inorganic chemistry.

[26]  Bingbing Liu,et al.  Isolation of three isomers of Sm@C84 and X-ray crystallographic characterization of Sm@D(3d)(19)-C84 and Sm@C2(13)-C84. , 2012, Journal of the American Chemical Society.

[27]  Z. Gu,et al.  Different Extraction Behaviors between Divalent and Trivalent Endohedral Metallofullerenes , 2004 .

[28]  Takeshi Akasaka,et al.  Structural determination of metallofullerene Sc3C82 revisited: a surprising finding. , 2005, Journal of the American Chemical Society.

[29]  Wei Xu,et al.  Planar quinary cluster inside a fullerene cage: synthesis and structural characterizations of Sc(3)NC@C(80)-I(h). , 2010, Journal of the American Chemical Society.

[30]  Luis Echegoyen,et al.  Large metal ions in a relatively small fullerene cage: the structure of Gd3N@C2(22010)-C78 departs from the isolated pentagon rule. , 2009, Journal of the American Chemical Society.

[31]  Panos P. Fatouros,et al.  Metallofullerene-based nanoplatform for brain tumor brachytherapy and longitudinal imaging in a murine orthotopic xenograft model. , 2011, Radiology.

[32]  Xing Lu,et al.  Crystallographic X-ray analyses of Yb@C(2v)(3)-C80 reveal a feasible rule that governs the location of a rare earth metal inside a medium-sized fullerene. , 2011, Journal of the American Chemical Society.

[33]  R. Smalley,et al.  Fullerenes with metals inside , 1991 .

[34]  J. Morton,et al.  A cyclic porphyrin trimer as a receptor for fullerenes. , 2010, Organic letters.

[35]  E. Campbell,et al.  Thermal stability of Li@C60 , 1999 .

[36]  Z. Gu,et al.  Reactions of endohedral metallofullerenes with azomethine ylides: an efficient route toward metallofullerene-pyrrolidines , 2004 .

[37]  S. P. Rath,et al.  Pyramidalization of Gd3N inside a C80 cage. The synthesis and structure of Gd3N@C80. , 2004, Chemical communications.

[38]  Feng Zhu,et al.  Chlorofullerenes featuring triple sequentially fused pentagons. , 2010, Nature chemistry.

[39]  Paul C. Wang,et al.  The scavenging of reactive oxygen species and the potential for cell protection by functionalized fullerene materials. , 2009, Biomaterials.

[40]  L. Echegoyen,et al.  Unexpected chemical and electrochemical properties of M3N@C80 (M = Sc, Y, Er). , 2006, Journal of the American Chemical Society.

[41]  S. Iijima,et al.  Real time reaction dynamics in carbon nanotubes. , 2001, Journal of the American Chemical Society.

[42]  B. Sitharaman,et al.  Understanding paramagnetic relaxation phenomena for water-soluble gadofullerenes , 2007 .

[43]  L. Echegoyen,et al.  A simple isomeric separation of D5h and Ih Sc3N@C80 by selective chemical oxidation. , 2005, Journal of the American Chemical Society.

[44]  KashinoSetsuo,et al.  Extractions of Ca@C60 and Sr@C60 with Aniline , 1996 .

[45]  J. Alford,et al.  Chemical oxidation of endohedral metallofullerenes: identification and separation of distinct classes. , 2003, Chemical communications.

[46]  Shangfeng Yang,et al.  A large family of dysprosium-based trimetallic nitride endohedral fullerenes: Dy3N@C2n (39 , 2005, The journal of physical chemistry. B.

[47]  A. Popov,et al.  Bonding in endohedral metallofullerenes as studied by quantum theory of atoms in molecules. , 2009, Chemistry.

[48]  T. Mizutani,et al.  Enhanced 1520 nm photoluminescence from Er3+ ions in di-erbium-carbide metallofullerenes (Er2C2)@C82 (isomers I, II, and III). , 2007, ACS nano.

[49]  S. Stevenson,et al.  Nonchromatographic "stir and filter approach" (SAFA) for isolating Sc3N@C80 metallofullerenes. , 2006, Journal of the American Chemical Society.

[50]  D. Guldi,et al.  Metal nitride cluster fullerene M3N@C80 (M=Y, Sc) based dyads: synthesis, and electrochemical, theoretical and photophysical studies. , 2009, Chemistry.

[51]  Martin Saunders,et al.  Stable Compounds of Helium and Neon: He@C60 and Ne@C60 , 1993, Science.

[52]  L. Echegoyen,et al.  Reactivity of metallic nitride endohedral metallofullerene anions: electrochemical synthesis of a Lu3N@Ih-C80 derivative. , 2011, Journal of the American Chemical Society.

[53]  Zhu-de Xu,et al.  Production and Isolation of Ca@C82 (I−IV) and Ca@C84 (I,II) Metallofullerenes , 1996 .

[54]  Lothar Dunsch,et al.  Metal sulfide in a C82 fullerene cage: a new form of endohedral clusterfullerenes. , 2010, Journal of the American Chemical Society.

[55]  Z. Gu,et al.  High-yield preparation of endohedral metallofullerenes by an improved DC arc-discharge method , 2000 .

[56]  S. Nagase,et al.  La@C82 Anion. An Unusually Stable Metallofullerene , 2000 .

[57]  Koichi Kikuchi,et al.  Characterization of the Isolated Y@C82 , 1994 .

[58]  M. Sakata,et al.  Sc2 dimer in IPR-violated C66 fullerene: a covalent bonded metallofullerene , 2003 .

[59]  Tianming Zuo,et al.  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 Tm3+ ions. , 2008, Inorganic chemistry.

[60]  Lothar Dunsch,et al.  Structure, stability, and cluster-cage interactions in nitride clusterfullerenes M3N@C2n (M = Sc, Y; 2n = 68-98): a density functional theory study. , 2007, Journal of the American Chemical Society.

[61]  C. Beavers,et al.  A seven atom cluster in a carbon cage, the crystallographically determined structure of Sc4(mu3-O)3@Ih-C80. , 2010, Chemical communications.

[62]  Y. Lian,et al.  Selective extraction and purification of endohedral metallofullerene from carbon soot. , 2006, The journal of physical chemistry. B.

[63]  S. Nagase,et al.  Synthesis and characterization of a bisadduct of La@C82. , 2006, Journal of the American Chemical Society.

[64]  Xing Lu,et al.  X-ray structures of Sc2C2@C2n (n = 40-42): in-depth understanding of the core-shell interplay in carbide cluster metallofullerenes. , 2012, Inorganic chemistry.

[65]  S. Nagase,et al.  Regioselective bis-functionalization of endohedral dimetallofullerene, La2@C80: extremal La-La distance. , 2011, Journal of the American Chemical Society.

[66]  P. Fatouros,et al.  Encapsulation of a radiolabeled cluster inside a fullerene cage, (177)Lu(x)Lu((3-x))N@C(80): an interleukin-13-conjugated radiolabeled metallofullerene platform. , 2010, Journal of the American Chemical Society.

[67]  Shangfeng Yang,et al.  A facile route to metal nitride clusterfullerenes by using guanidinium salts: a selective organic solid as the nitrogen source. , 2010, Chemistry.

[68]  P. Fatouros,et al.  In vitro and in vivo imaging studies of a new endohedral metallofullerene nanoparticle. , 2006, Radiology.

[69]  L. Echegoyen,et al.  Trimetallic nitride endohedral metallofullerenes: reactivity dictated by the encapsulated metal cluster. , 2005, Journal of the American Chemical Society.

[70]  L. Weng,et al.  Electronic Structure of Ce@C82: An Experimental Study , 1996 .

[71]  T. Uruga,et al.  Electronic structure of Eu@C60 studied by XANES and UV–VIS absorption spectra , 2000 .

[72]  Xing Lu,et al.  Radical derivatives of insoluble La@C74: X-ray structures, metal positions, and isomerization. , 2011, Angewandte Chemie.

[73]  S. Nagase,et al.  La@C72 having a non-IPR carbon cage. , 2006, Journal of the American Chemical Society.

[74]  Xing Lu,et al.  Yb@C2n (n = 40, 41, 42): new fullerene allotropes with unexplored electrochemical properties. , 2010, Journal of the American Chemical Society.

[75]  Shangfeng Yang,et al.  Titanium/yttrium mixed metal nitride clusterfullerene TiY2N@C80: synthesis, isolation, and effect of the group-III metal. , 2012, Inorganic chemistry.

[76]  David E. Luzzi,et al.  Tumbling atoms and evidence for charge transfer in La2@C80@SWNT , 2000 .

[77]  Shuying Liu,et al.  Synthesis and solvent enhanced relaxation property of water-soluble endohedral metallofullerenols , 1997 .

[78]  D. Guldi,et al.  Covalently linked porphyrin-La@C82 hybrids: structural elucidation and investigation of intramolecular interactions. , 2011, Angewandte Chemie.

[79]  T. Okazaki,et al.  Trapping a C2 radical in endohedral metallofullerenes: Synthesis and structures of (Y2C2)@C82 (isomers I, II, and III) , 2004 .

[80]  Y. Achiba,et al.  Electrochemical properties of fullerenolanthanides , 1996 .

[81]  S. Nagase,et al.  Isolation and characterization of two Pr@C82 isomers , 2000 .

[82]  S. Nagase,et al.  Positional control of encapsulated atoms inside a fullerene cage by exohedral addition. , 2005, Journal of the American Chemical Society.

[83]  Masahiro Kondo,et al.  Isolation, characterization, and theoretical study of La2@C78. , 2004, Journal of the American Chemical Society.

[84]  Hisanori Shinohara,et al.  Structure of a missing-caged metallofullerene: La2@C72. , 2003, Journal of the American Chemical Society.

[85]  Steven Stevenson,et al.  The shape of the Sc2(μ2-S) unit trapped in C82: crystallographic, computational, and electrochemical studies of the isomers, Sc2(μ2-S)@C(s)(6)-C82 and Sc2(μ2-S)@C(3v)(8)-C82. , 2011, Journal of the American Chemical Society.

[86]  A. Balch,et al.  Sc3N@C68: folded pentalene coordination in an endohedral fullerene that does not obey the isolated pentagon rule. , 2003, Angewandte Chemie.

[87]  D. Guldi,et al.  Stable radical anions inside fullerene cages: formation of reversible electron transfer systems. , 2011, Journal of the American Chemical Society.

[88]  T. Aida,et al.  Ferromagnetic spin coupling between endohedral metallofullerene La@C82 and a cyclodimeric copper porphyrin upon inclusion. , 2011, Journal of the American Chemical Society.

[89]  S. Nagase,et al.  Regioselective exohedral functionalization of La@C82 and its 1,2,3,4,5-pentamethylcyclopentadiene and adamantylidene adducts. , 2010, Chemistry.

[90]  Marcel Swart,et al.  Product formation in the Prato reaction on Sc3N@D(5h)-C80: preference for [5,6]-bonds, and not pyracylenic bonds. , 2012, Chemical communications.

[91]  L. Echegoyen,et al.  Synthesis and electrochemical studies of Bingel-Hirsch derivatives of M(3)N@I(h)-C(80) (M=Sc, Lu). , 2010, Chemistry.

[92]  S. Nagase,et al.  Lanthanum endohedral metallofulleropyrrolidines: synthesis, isolation, and EPR characterization. , 2004, Chemistry.

[93]  S. Strauss,et al.  Sc3N@(C80-Ih7)(CF3)14 and Sc3N@(C80-Ih(7))(CF3)16. Endohedral metallofullerene derivatives with exohedral addends on four and eight triple-hexagon junctions. Does the Sc3N cluster control the addition pattern or vice versa? , 2009, Journal of the American Chemical Society.

[94]  G. P. Moss,et al.  Nomenclature for the C60-Ih and C70-D5h(6) fullerenes (IUPAC Recommendations 2002) , 2002 .

[95]  J. Warner,et al.  Rotating fullerene chains in carbon nanopeapods. , 2008, Nano letters.

[96]  R. Lauffer,et al.  Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications. , 1999, Chemical reviews.

[97]  A. Balch,et al.  Isolation of four isomers of C96 and crystallographic characterization of nanotubular D3d(3)-C96 and the somewhat flat-sided sphere C2(181)-C96. , 2012, Chemistry.

[98]  W. Xu,et al.  Entrapped Planar Trimetallic Carbide in a Fullerene Cage: Synthesis, Isolation, and Spectroscopic Studies of Lu3C2@C88 , 2011 .

[99]  Zdenek Slanina,et al.  Chemical understanding of a non-IPR metallofullerene: stabilization of encaged metals on fused-pentagon bonds in La2@C72. , 2008, Journal of the American Chemical Society.

[100]  S. Lebedkin,et al.  ESR spectra of endohedral metallofullerene Ce@C82 radical anions in dimethylformamide and pyridine , 2003 .

[101]  S. Nagase,et al.  Regioselective cycloaddition of La2@I(h)-C80 with tetracyanoethylene oxide: formation of an endohedral dimetallofullerene adduct featuring enhanced electron-accepting character. , 2011, Journal of the American Chemical Society.

[102]  S. Nagase,et al.  Does Gd@C82 have an anomalous endohedral structure? Synthesis and single crystal X-ray structure of the carbene adduct. , 2008, Journal of the American Chemical Society.

[103]  Matthias Krause,et al.  Expanding the world of endohedral fullerenes--the Tm3N@C2n (39< or =n< or =43) clusterfullerene family. , 2005, Chemistry.

[104]  S. Nagase,et al.  Radical coupling reaction of paramagnetic endohedral metallofullerene La@C82. , 2008, Journal of the American Chemical Society.

[105]  Xu Zhang,et al.  Capturing the Labile Fullerene[50] as C50Cl10 , 2004, Science.

[106]  W. H. Powell,et al.  Numbering of Fullerenes (IUPAC Recommendations 2004) , 2005 .

[107]  Wujun Fu,et al.  14N and 45Sc NMR study of trimetallic nitride cluster (M3N)6+ dynamics inside a icosahedral C80 cage. , 2011, Chemical communications.

[108]  A. Fisher,et al.  Small-bandgap endohedral metallofullerenes in high yield and purity , 1999, Nature.

[109]  S. Nagase,et al.  Supramolecular complexes of La@C82 with unsaturated thiacrown ethers. , 2006, Chemical communications.

[110]  Tianming Zuo,et al.  89Y and 13C NMR cluster and carbon cage studies of an yttrium metallofullerene family, Y3N@C(2n) (n = 40-43). , 2009, Journal of the American Chemical Society.

[111]  Z. Gu,et al.  Selective reduction and extraction of Gd@C82 and Gd2@C80 from soot and the chemical reaction of their anions , 2005 .

[112]  C. Beavers,et al.  Very large, soluble endohedral fullerenes in the series La2C90 to La2C138: isolation and crystallographic characterization of La2@D5(450)-C100. , 2011, Journal of the American Chemical Society.

[113]  S. Nagase,et al.  Sc2@C70 rather than Sc2C2@C68: density functional theory characterization of metallofullerene Sc2C70. , 2012, The Journal of chemical physics.

[114]  L. Echegoyen,et al.  "Open rather than closed" malonate methano-fullerene derivatives. The formation of methanofulleroid adducts of Y3N@C80. , 2007, Journal of the American Chemical Society.

[115]  A. Balch,et al.  Preparation and structure of CeSc2N@C80: an icosahedral carbon cage enclosing an acentric CeSc2N unit with buried f electron spin. , 2006, Journal of the American Chemical Society.

[116]  Houjin Huang,et al.  Relative yields of endohedral lanthanide metallofullerenes by arc synthesis and their correlation with the elution behavior , 1998 .

[117]  S. Kennel,et al.  (212)Pb@C(60) and its water-soluble derivatives: synthesis, stability, and suitability for radioimmunotherapy. , 2007, Journal of the American Chemical Society.

[118]  Michael M. Gottesman,et al.  Metallofullerene nanoparticles circumvent tumor resistance to cisplatin by reactivating endocytosis , 2010, Proceedings of the National Academy of Sciences.

[119]  J. S. Fu,et al.  The third-order non-linear optical response of the endohedral metallofullerene Dy@C82 , 1998 .

[120]  Tianming Zuo,et al.  New egg-shaped fullerenes: non-isolated pentagon structures of Tm3N@C(s)(51 365)-C84 and Gd3N@C(s)(51 365)-C84. , 2008, Chemical communications.

[121]  Li-Jun Wan,et al.  C64H4: production, isolation, and structural characterizations of a stable unconventional fulleride. , 2006, Journal of the American Chemical Society.

[122]  C. Beavers,et al.  Isolation and crystallographic identification of four isomers of Sm@C90. , 2011, Journal of the American Chemical Society.

[123]  Robert C. Haddon,et al.  C60 thin film transistors , 1995 .

[124]  S. Kennel,et al.  In vivo studies of fullerene-based materials using endohedral metallofullerene radiotracers. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[125]  P. A. Brühwiler,et al.  Proof for trivalent Sc ions in Sc-2 @ C-84 from high-energy spectroscopy , 2000 .

[126]  Ian D. Williams,et al.  Synthesis of a Dy@C82 derivative bearing a single phosphorus substituent via a zwitterion approach. , 2007, Journal of the American Chemical Society.

[127]  Takeshi Akasaka,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. , 2009, Chemistry.

[128]  Zdenek Slanina,et al.  Addition of adamantylidene to La2@C78: isolation and single-crystal X-ray structural determination of the monoadducts. , 2008, Journal of the American Chemical Society.

[129]  Z. Chai,et al.  Antioxidative function and biodistribution of [Gd@C82(OH)22]n nanoparticles in tumor-bearing mice. , 2006, Biochemical pharmacology.

[130]  S. Nagase,et al.  Two-dimensional hopping motion of encapsulated La atoms in silylated La(2)@C(80). , 2007, Chemical communications.

[131]  P. Ballester,et al.  Complexation of Sc3N@C80 endohedral fullerene with cyclic Zn-bisporphyrins: solid state and solution studies. , 2011, The Journal of organic chemistry.

[132]  S. Stevenson,et al.  Preferential encapsulation and stability of La(3)N cluster in 80 atom cages: experimental synthesis and computational investigation of La(3)N@C(79)N. , 2009, Journal of the American Chemical Society.

[133]  Panos P. Fatouros,et al.  High relaxivity trimetallic nitride (Gd3N) metallofullerene MRI contrast agents with optimized functionality. , 2010, Bioconjugate chemistry.

[134]  Xing-Jie Liang,et al.  Inhibition of Tumor Growth by Endohedral Metallofullerenol Nanoparticles Optimized as Reactive Oxygen Species Scavenger , 2008, Molecular Pharmacology.

[135]  S. Nagase,et al.  Semi-metallic single-component crystal of soluble La@C82 derivative with high electron mobility. , 2011, Journal of the American Chemical Society.

[136]  D. Bethune,et al.  Preparation and structure of crystals of the metallofullerene Sc2@C84 , 1994, Nature.

[137]  S. Strauss,et al.  Radical trifluoromethylation of Sc3N@C80. , 2007, Journal of the American Chemical Society.

[138]  Zhennan Gu,et al.  ISOLATION AND SPECTROSCOPIC STUDY OF A SERIES OF MONOTERBIUM ENDOHEDRAL METALLOFULLERENES , 2002 .

[139]  Hisanori Shinohara,et al.  Determination of the cage structure of Sc@C82 by synchrotron powder diffraction , 1998 .

[140]  Chunru Wang,et al.  Syntheses and structures of phenyl-C81-butyric acid methyl esters (PCBMs) from M3N@C80. , 2009, Organic letters.

[141]  Y. Lian,et al.  Synthesis and characterization of exohedrally silylated M@C82 (M = Y and La). , 2005, The journal of physical chemistry. B.

[142]  S. Nagase,et al.  Theoretical study of the lanthanide fullerene CeC82. Comparison with ScC82, YC82 and LaC82 , 1994 .

[143]  Kazunori Yamamoto,et al.  Isolation of an ESR-Active Metallofullerene of La@C82 , 1994 .

[144]  Y. Lian,et al.  Analysis of lanthanide-induced NMR shifts of the Ce@C82 anion. , 2006, Journal of the American Chemical Society.

[145]  S. Strauss,et al.  Poly(perfluoroalkylation) of metallic nitride fullerenes reveals addition-pattern guidelines: synthesis and characterization of a family of Sc3N@C80(CF3)n (n = 2-16) and their radical anions. , 2011, Journal of the American Chemical Society.

[146]  C. Beavers,et al.  Large endohedral fullerenes containing two metal ions, Sm2@D2(35)-C88, Sm2@C1(21)-C90, and Sm2@D3(85)-C92, and their relationship to endohedral fullerenes containing two gadolinium ions. , 2011, Journal of the American Chemical Society.

[147]  S. Nagase,et al.  Chemical derivatization of endohedral metallofullerene La@C82 with digermirane , 1996 .

[148]  Y. Murata,et al.  Surgery of fullerenes. , 2008, Chemical communications.

[149]  S. Nagase,et al.  Missing metallofullerene with C80 cage. , 2009, Journal of the American Chemical Society.

[150]  A. Rodríguez‐Fortea,et al.  Endohedral metallofullerenes: a unique host-guest association. , 2011, Chemical Society reviews.

[151]  A. Popov,et al.  A pseudoatom in a cage: trimetallofullerene Y(3)@C(80) mimics y(3)n@c(80) with nitrogen substituted by a pseudoatom. , 2010, ACS nano.

[152]  A. Balch,et al.  Isolation and structural characterization of the molecular nanocapsule Sm(2)@D(3d)(822)-C(104). , 2009, Angewandte Chemie.

[153]  Xing Lu,et al.  Dichlorophenyl derivatives of La@C(3v)(7)-C(82): endohedral metal induced localization of pyramidalization and spin on a triple-hexagon junction. , 2010, Angewandte Chemie.

[154]  S. Iijima,et al.  One-dimensional metallofullerene crystal generated inside single-walled carbon nanotubes. , 2000, Physical review letters.

[155]  A. Balch,et al.  Crystallographic characterization of the structure of the endohedral fullerene [Er2@C82 isomer I] with C(s) cage symmetry and multiple sites for erbium along a band of ten contiguous hexagons. , 2002, Journal of the American Chemical Society.

[156]  S. C. O'brien,et al.  Lanthanum complexes of spheroidal carbon shells , 1985 .

[157]  A. Vlaicu,et al.  Charge transfer satellite in Pr @ C 82 metallofullerene observed using resonant x-ray emission spectroscopy , 2009 .

[158]  W. Krätschmer,et al.  Solid C60: a new form of carbon , 1990, Nature.

[159]  S. Saito,et al.  Growth mechanism and geometry of LaC82 , 1992 .

[160]  S. Iijima,et al.  High-resolution electron microscopy of individual metallofullerene molecules on the dipole orientations in peapods , 2003 .

[161]  Chunru Wang,et al.  Synthesis and characterization of a new water-soluble endohedral metallofullerene for MRI contrast agents , 2006 .

[162]  Y. Saito,et al.  High yield synthesis of lanthanofullerenes via lanthanum carbide , 1993 .

[163]  A. Hirsch,et al.  Fullerene Chemistry in Three Dimensions: Isolation of Seven Regioisomeric Bisadducts and Chiral Trisadducts of C60 and Di(ethoxycarbonyl)methylene , 1994 .

[164]  Junfeng Zhang,et al.  Theoretical study on the motion of a La atom inside a C82 cage. , 2007, The journal of physical chemistry. A.

[165]  Y. Achiba,et al.  Structural study of three isomers of Tm@C(82) by (13)C NMR spectroscopy. , 2002, Journal of the American Chemical Society.

[166]  Martin Saunders,et al.  Noble Gas Atoms Inside Fullerenes , 1996, Science.

[167]  I. V. Hertel,et al.  Endohedral fullerene production , 1996, Nature.

[168]  S. Nagase,et al.  Anisotropic magnetic behavior of anionic Ce@C82 carbene adducts. , 2009, Journal of the American Chemical Society.

[169]  T. Okazaki,et al.  Bandgap modulation of carbon nanotubes by encapsulated metallofullerenes , 2002, Nature.

[170]  Yusuke Nakanishi,et al.  Closed network growth of fullerenes , 2012, Nature Communications.

[171]  Xing Lu,et al.  Soluble and tubular higher fullerenes that encapsulate metals. , 2012, Angewandte Chemie.

[172]  Chunru Wang,et al.  Metallofullerenes Sc2@C82(I, II) and Sc2@C86(I, II): isolation and spectroscopic studies , 1999 .

[173]  Z. Gu,et al.  Addition of Benzyne to Gd@C82 , 2004 .

[174]  J. Fettinger,et al.  A pirouette on a metallofullerene sphere: interconversion of isomers of N-tritylpyrrolidino I(h) Sc3N@C80. , 2006, Journal of the American Chemical Society.

[175]  Houjin Huang,et al.  Toward Efficient Synthesis of Endohedral Metallofullerenes by Arc Discharge of Carbon Rods Containing Encapsulated Rare Earth Carbides and Ultrasonic Soxhlet Extraction , 2000 .

[176]  Marcel Swart,et al.  Chemical reactivity of D3h C78 (metallo)fullerene: regioselectivity changes induced by Sc3N encapsulation. , 2008, Journal of the American Chemical Society.

[177]  S. Stevenson,et al.  Effect of copper metal on the yield of Sc3N@C80 metallofullerenes. , 2007, Chemical communications.

[178]  S. Nagase,et al.  Metal atoms collinear with the spiro carbon of 6,6-open adducts, M2@C80(Ad) (M = La and Ce, Ad = adamantylidene). , 2008, Journal of the American Chemical Society.

[179]  Shangfeng Yang,et al.  - 1-Electronic Supplementary Information ( ESI ) for : An Endohed r al Titanium ( III ) in a Clusterfullerene : Putting a Non-Group-III Metal Nitride into the C 80-Ih Fullerene Cage , 2009 .

[180]  C. Beavers,et al.  Isolation of a small carbon nanotube: the surprising appearance of D(5h)(1)-C(90). , 2010, Angewandte Chemie.

[181]  A. Balch,et al.  Preparation and crystallographic characterization of a new endohedral, Lu3N@C80.5 (o-xylene), and comparison with Sc3N@C80.5 (o-xylene). , 2002, Chemistry.

[182]  A. Chuvilin,et al.  Functionalised endohedral fullerenes in single-walled carbon nanotubes. , 2011, Chemical communications.

[183]  A. Weidinger,et al.  Atomic nitrogen in C60:N@C60 , 1998 .

[184]  S. Nagase,et al.  Ionization and structural determination of the major isomer of Pr@C82 , 2002 .

[185]  Robert F. Curl,et al.  The formation of long carbon chain molecules during laser vaporization of graphite , 1987 .

[186]  M. Gross,et al.  Isolation and Spectral Properties of Kr@C60, a Stable van der Waals Molecule , 1999 .

[187]  Chun-ying Shu,et al.  Aggregation studies of the water-soluble gadofullerene magnetic resonance imaging contrast agent: [Gd@C82O6(OH)16(NHCH2CH2COOH)8]x. , 2006, The journal of physical chemistry. B.

[188]  E. Nishibori,et al.  A layered ionic crystal of polar Li@C(60) superatoms. , 2010, Nature chemistry.

[189]  S. Emura,et al.  Extractions of Y@C60, Ba@C60, La@C60, Ce@C60, Pr@C60, Nd@C60, and Gd@C60 with Aniline , 1996 .

[190]  Marilyn M. Olmstead,et al.  Isolation and Structural Characterization of the Endohedral Fullerene Sc3N@C78 , 2001 .

[191]  S. Emura,et al.  Enrichment of Ce@C60 by HPLC Technique , 1996 .

[192]  S. Nagase,et al.  Chemical Modification of Endohedral Metallofullerene La@C82 with 3-chloro-3-phenyldiazirine , 2010 .

[193]  Houjin Huang,et al.  Langmuir–Blodgett films of the endohedral metallofullerene Dy@C82 at the air–water interface , 2000 .

[194]  Carsten Bingel,et al.  Cyclopropanierung von Fullerenen , 1993 .

[195]  D. Guldi,et al.  Photoinduced charge transfer and electrochemical properties of triphenylamine I(h)-Sc3N@C80 donor-acceptor conjugates. , 2009, Journal of the American Chemical Society.

[196]  Y. Maruyama,et al.  Electrochemistry and Ab Initio Study of the Dimetallofullerene La2@C80 , 1995 .

[197]  Shigeru Nagase,et al.  Endofullerenes : a new family of carbon clusters , 2002 .

[198]  Xing Lu,et al.  Structural and electronic properties of endohedral metallofullerenes. , 2012, Chemical record.

[199]  M. Sakata,et al.  Bent (metal)2C2 clusters encapsulated in (Sc2C2)@C82(III) and (Y2C2)@C82(III) metallofullerenes , 2006 .

[200]  S. Nagase,et al.  A stable unconventional structure of Sc2@C66 found by density functional calculations , 2002 .

[201]  D. Guldi,et al.  Donor-acceptor conjugates of lanthanum endohedral metallofullerene and pi-extended tetrathiafulvalene. , 2010, Journal of the American Chemical Society.

[202]  S. Iijima,et al.  Nanorods of endohedral metallofullerene derivative. , 2008, Journal of the American Chemical Society.

[203]  H. Shinohara,et al.  Paramagnetic water-soluble metallofullerenes having the highest relaxivity for MRI contrast agents. , 2001, Bioconjugate chemistry.

[204]  M. Wong,et al.  Destroying gadofullerene aggregates by salt addition in aqueous solution of Gd@C(60)(OH)(x) and Gd@C(60)[C(COOH(2))](10). , 2005, Journal of the American Chemical Society.

[205]  H. Gibson,et al.  Purification of endohedral trimetallic nitride fullerenes in a single, facile step. , 2005, Journal of the American Chemical Society.

[206]  E. Hajdu,et al.  Materials science: A stable non-classical metallofullerene family , 2000, Nature.

[207]  S. Nagase,et al.  ESR study on the reactivity of two isomers of LaC82 with disilirane , 1996 .

[208]  Shangfeng Yang,et al.  Carbon pyramidalization in fullerene cages induced by the endohedral cluster: non-scandium mixed metal nitride clusterfullerenes. , 2008, Angewandte Chemie.

[209]  H. Gibson,et al.  Synthesis and characterization of the first trimetallic nitride templated pyrrolidino endohedral metallofullerenes. , 2005, Chemical communications.

[210]  C. de Graaf,et al.  Electronic structure and redox properties of metal nitride endohedral fullerenes M(3)N@C(2n) (M=Sc, Y, La, and Gd; 2n=80, 84, 88, 92, 96). , 2009, Chemistry.

[211]  B. Sitharaman,et al.  Gd@C60[C(COOH)2]10 and Gd@C60(OH)x: Nanoscale Aggregation Studies of Two Metallofullerene MRI Contrast Agents in Aqueous Solution , 2004 .

[212]  Luis Echegoyen,et al.  Chemical, electrochemical, and structural properties of endohedral metallofullerenes. , 2009, Angewandte Chemie.

[213]  Tianming Zuo,et al.  Tb3N@C84: an improbable, egg-shaped endohedral fullerene that violates the isolated pentagon rule. , 2006, Journal of the American Chemical Society.

[214]  Roger Taylor,et al.  Isolation of Two Seven-Membered Ring C58 Fullerene Derivatives: C58F17CF3 and C58F18 , 2005, Science.

[215]  Rong-Bin Huang,et al.  C72Cl4: a pristine fullerene with favorable pentagon-adjacent structure. , 2010, Journal of the American Chemical Society.

[216]  A. Balch,et al.  Crystallographic characterization and structural analysis of the first organic functionalization product of the endohedral fullerene Sc(3)N@C(80). , 2002, Journal of the American Chemical Society.

[217]  Yuji Kobayashi,et al.  Materials science: C66 fullerene encaging a scandium dimer , 2000, Nature.

[218]  Shangfeng Yang,et al.  Spin-flow vibrational spectroscopy of molecules with flexible spin density: electrochemistry, ESR, cluster and spin dynamics, and bonding in TiSc2N@C80. , 2010, ACS nano.

[219]  R. D. Bolskar Gadofullerene MRI contrast agents. , 2008, Nanomedicine.

[220]  Sílvia Osuna,et al.  The Diels-Alder reaction on endohedral Y3N@C78: the importance of the fullerene strain energy. , 2009, Journal of the American Chemical Society.

[221]  M. Sakata,et al.  Giant motion of La atom inside C82 cage , 2000 .

[222]  E. Kemnitz,et al.  New trifluoromethylated derivatives of [60]fullerene, C60(CF3)n with n = 12 and 14. , 2007, Chemical communications.

[223]  A. Popov,et al.  Hindered cluster rotation and 45Sc hyperfine splitting constant 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. , 2008, Journal of the American Chemical Society.

[224]  Y. Maruyama,et al.  Isolation and Characterization of an ESR-Active La@C82 Isomer , 1994 .

[225]  M. Sakata,et al.  A Scandium Carbide Endohedral Metallofullerene: (Sc2 C2 )@C84. , 2001, Angewandte Chemie.

[226]  Christopher G. Rylander,et al.  In vitro and in vivo studies of single-walled carbon nanohorns with encapsulated metallofullerenes and exohedrally functionalized quantum dots. , 2010, Nano letters.

[227]  Marilyn M. Olmstead,et al.  Isolation and Crystallographic Characterization of ErSc2N@C80: an Endohedral Fullerene Which Crystallizes with Remarkable Internal Order , 2000 .

[228]  S. Jockusch,et al.  Can H2 inside C60 communicate with the outside world? , 2007, Journal of the American Chemical Society.

[229]  Takeshi Akasaka,et al.  Unconventional cage structures of endohedral metallofullerenes , 1999 .

[230]  S. Nagase,et al.  Strong metal-cage hybridization in endohedral La@C82, Y@C82 and Sc@C82 , 2000 .

[231]  K. Ohkubo,et al.  Strong supramolecular binding of Li(+)@C60 with sulfonated meso-tetraphenylporphyrins and long-lived photoinduced charge separation. , 2012, Chemical communications.

[232]  T. Lewis,et al.  Crystal Structure of Osmylated C60: Confirmation of the Soccer Ball Framework , 1991, Science.

[233]  Jiechao Ge,et al.  Nanoscale fullerene compression of an yttrium carbide cluster. , 2012, Journal of the American Chemical Society.

[234]  T. Sugai,et al.  Spectroscopic and structural study of Y2C2 carbide encapsulating endohedral metallofullerene: (Y2C2)@C82 , 2003 .

[235]  Takeshi Akasaka,et al.  Experimental and theoretical studies of the scandium carbide endohedral metallofullerene Sc2C2@C82 and its carbene derivative. , 2007, Angewandte Chemie.

[236]  J. Morton,et al.  Electron spin coherence in metallofullerenes: Y, Sc, and La@C82 , 2010, 1002.1282.

[237]  S. Nagase,et al.  Metallofullerenes MC82 (M = Sc, Y, and La). A theoretical study of the electronic and structural aspects , 1993 .

[238]  S. Nagase,et al.  Synthesis and characterization of tetrakis-silylated C60 isomers. , 2003, The Journal of organic chemistry.

[239]  Carlo Thilgen,et al.  Structural aspects of fullerene chemistry--a journey through fullerene chirality. , 2006, Chemical reviews.

[240]  Ting Cai,et al.  Sc3N@C78: encapsulated cluster regiocontrol of adduct docking on an ellipsoidal metallofullerene sphere. , 2007, Journal of the American Chemical Society.

[241]  Shangfeng Yang,et al.  C76 fullerene chlorides and cage transformations. Structural and theoretical study. , 2011, Dalton transactions.

[242]  Matthias Krause,et al.  C78 cage isomerism defined by trimetallic nitride cluster size: a computational and vibrational spectroscopic study. , 2007, The journal of physical chemistry. B.

[243]  A. Rao,et al.  Lanthanum nitride endohedral fullerenes La3N@C2n (43 , 2008, Chemistry.

[244]  Zdenek Slanina,et al.  Chemical understanding of carbide cluster metallofullerenes: a case study on Sc2C2@C2v(5)-C80 with complete X-ray crystallographic characterizations. , 2012, Journal of the American Chemical Society.

[245]  H. Kroto,et al.  The smallest stable fullerene, M@C28 (m = Ti, Zr, U): stabilization and growth from carbon vapor. , 2012, Journal of the American Chemical Society.

[246]  A. Balch,et al.  Detection of a family of gadolinium-containing endohedral fullerenes and the isolation and crystallographic characterization of one member as a metal-carbide encapsulated inside a large fullerene cage. , 2008, Journal of the American Chemical Society.

[247]  J. Campanera,et al.  Bonding within the Endohedral Fullerenes Sc3N@C78 and Sc3N@C80 as Determined by Density Functional Calculations and Reexamination of the Crystal Structure of {Sc3N@C78}·Co(OEP)}·1.5(C6H6)·0.3(CHCl3) , 2002 .

[248]  Z. Gu,et al.  Intrafullerene electron transfers in Sm-containing metallofullerenes: Sm@C2n (74 < or = 2n < or = 84). , 2001, Journal of molecular graphics & modelling.

[249]  C. Beavers,et al.  Isolation and structural characterization of two very large, and largely empty, endohedral fullerenes: Tm@C(3v)-C(94) and Ca@C(3v)-C(94). , 2009, Inorganic chemistry.

[250]  S. Nagase,et al.  Exohedral derivatization of an endohedral metallofullerene Gd@C82 , 1995 .

[251]  Takeshi Akasaka,et al.  A molecular Ce2@I(h)-C80 switch--unprecedented oxidative pathway in photoinduced charge transfer reactivity. , 2010, Journal of the American Chemical Society.

[252]  S. Nagase,et al.  Spectroscopic and theoretical study of endohedral dimetallofullerene having a non-IPR fullerene cage: Ce2@C72. , 2008, The journal of physical chemistry. A.

[253]  J. Morton,et al.  Environmental effects on electron spin relaxation in N @ C 60 , 2006, quant-ph/0611108.

[254]  K. Kitazawa,et al.  Crystallographic characterization of Kr@C60 in (0.09Kr@C60/0.91C60). (NiII(OEP)).2C6H6. , 2002, Chemical communications.

[255]  S. Nagase,et al.  Isolation and characterization of a carbene derivative of La@C82. , 2004, Journal of the American Chemical Society.

[256]  Y. Achiba,et al.  Synthesis of the First Adducts of the Dimetallofullerenes La2@C80 and Sc2@C84 by Addition of a Disilirane , 1995 .

[257]  Ning Chen,et al.  Synthesis of a new endohedral fullerene family, Sc2S@C2n (n = 40-50) by the introduction of SO2. , 2010, Chemical communications.

[258]  Ning Chen,et al.  Sc2S@C(s)(10528)-C72: a dimetallic sulfide endohedral fullerene with a non isolated pentagon rule cage. , 2012, Journal of the American Chemical Society.

[259]  Stephen R. Wilson,et al.  Hydrochalarones: a novel endohedral metallofullerene platform for enhancing magnetic resonance imaging contrast. , 2008, Journal of medicinal chemistry.

[260]  Feng Zhao,et al.  Multihydroxylated [Gd@C82(OH)22]n nanoparticles: antineoplastic activity of high efficiency and low toxicity. , 2005, Nano letters.

[261]  Y. Murata,et al.  Encapsulation and dynamic behavior of two H2 molecules in an open-cage C70. , 2008, Journal of the American Chemical Society.

[262]  Emmanuel Koudoumas,et al.  Third-Order Susceptibility of Li@C60 , 1999 .

[263]  Susie M. Miller,et al.  Synthesis, structure, and 19F NMR spectra of 1,3,7,10,14,17,23,28,31,40-C60(CF3)10. , 2005, Journal of the American Chemical Society.

[264]  T. Crawford,et al.  M2@C79N (M = Y, Tb): isolation and characterization of stable endohedral metallofullerenes exhibiting M-M bonding interactions inside aza[80]fullerene cages. , 2008, Journal of the American Chemical Society.

[265]  Y. Kubozono Preparation and EXtraction of Ca@C2602(共著) , 1995 .

[266]  Chunru Wang,et al.  Electrochemistry of Sc3N@C78 and Sc3N@C80 (Ih): On achieving reversible redox waves of the trimetal nitride endohedral fullerenes , 2007 .

[267]  S. Nagase,et al.  Structural Determination of the La@C82 Isomer , 2001 .

[268]  Lothar Dunsch,et al.  The role of an asymmetric nitride cluster on a fullerene cage: the non-IPR endohedral DySc2N@C76. , 2007, The journal of physical chemistry. B.

[269]  Xing Lu,et al.  Sc2@C3v(8)-C82 vs. Sc2C2@C3v(8)-C82: drastic effect of C2 capture on the redox properties of scandium metallofullerenes. , 2012, Chemical communications.

[270]  S. Nagase,et al.  Exohedral adducts of La@C82 , 1995, Nature.

[271]  Li Jiang,et al.  Synthesis, Isolation, Characterization, and Theoretical Studies of Sc3NC@C78-C2 , 2011 .

[272]  S. Nagase,et al.  13C NMR spectroscopic study of scandium dimetallofullerene, Sc2@C84 vs. Sc2C2@C82. , 2006, Chemical communications.

[273]  S. Nagase,et al.  Chemical reactivity of sc3n @ c80 and la2 @ c80. , 2005, Journal of the American Chemical Society.

[274]  Xing Lu,et al.  The long-believed Sc2@C(2v)(17)-C84 is actually Sc2C2@C(2v)(9)-C82: unambiguous structure assignment and chemical functionalization. , 2012, Angewandte Chemie.

[275]  Hua Guo,et al.  [Gd@C(82)(OH)(22)](n) nanoparticles induce dendritic cell maturation and activate Th1 immune responses. , 2010, ACS nano.

[276]  Marilyn M. Olmstead,et al.  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 , 2007 .

[277]  Luis Echegoyen,et al.  Gd3N@C2n (n = 40, 42, and 44): remarkably low HOMO-LUMO gap and unusual electrochemical reversibility of Gd3N@C88 . , 2007, Journal of the American Chemical Society.

[278]  S. Kubuki,et al.  Non-HPLC rapid separation of metallofullerenes and empty cages with TiCl4 Lewis acid. , 2012, Journal of the American Chemical Society.

[279]  G. Briggs,et al.  Molecular motion of endohedral fullerenes in single-walled carbon nanotubes. , 2004, Angewandte Chemie.

[280]  M. Sakata,et al.  Pentagonal-dodecahedral la2 charge density in [80-ih ]fullerene: la2 @c80. , 2001, Angewandte Chemie.

[281]  S. Stevenson,et al.  Selective complexation and reactivity of metallic nitride and oxometallic fullerenes with Lewis acids and use as an effective purification method. , 2009, Inorganic chemistry.

[282]  Marilyn M. Olmstead,et al.  Is the isolated pentagon rule merely a suggestion for endohedral fullerenes? The structure of a second egg-shaped endohedral fullerene--Gd3N@C(s)(39663)-C82. , 2008, Journal of the American Chemical Society.

[283]  Shangfeng Yang,et al.  The spin state of a charged non-IPR fullerene: the stable radical cation of Sc3N@C68. , 2007, Chemical communications.

[284]  C Colliex,et al.  Element-selective single atom imaging. , 2000, Science.

[285]  Y. Lian,et al.  The Bingel monoadducts of La@C82: synthesis, characterization, and electrochemistry. , 2006, Chemistry.

[286]  S. Nagase,et al.  Reversible and regioselective reaction of La@C82 with cyclopentadiene. , 2005, Journal of the American Chemical Society.

[287]  R. Whetten,et al.  Fullerene Isomerism: Isolation of C2v,-C78 and D3-C78 , 1991, Science.

[288]  C. Anklin,et al.  Selective formation of a symmetric Sc3N@C78 bisadduct: adduct docking controlled by an internal trimetallic nitride cluster. , 2008, Journal of the American Chemical Society.

[289]  A. Balch,et al.  Partial Separation and Structural Characterization of C84 Isomers by Crystallization of (.eta.2-C84)Ir(CO)Cl(P(C6H5)3)2 , 1994 .

[290]  Xing Lu,et al.  Where does the metal cation stay in Gd@C2v(9)-C82? A single-crystal X-ray diffraction study. , 2012, Inorganic chemistry.

[291]  Zdenek Slanina,et al.  Structural elucidation and regioselective functionalization of an unexplored carbide cluster metallofullerene Sc2C2@C(s)(6)-C82. , 2011, Journal of the American Chemical Society.

[292]  B. Holloway,et al.  Tuning Conversion Efficiency in Metallo Endohedral Fullerene‐Based Organic Photovoltaic Devices , 2009 .

[293]  R. Haddon C70 THIN FILM TRANSISTORS , 1996 .

[294]  L. Echegoyen,et al.  [2 + 2] cycloaddition reaction to Sc3N@I(h)-C80. The formation of very stable [5,6]- and [6,6]-adducts. , 2011, Journal of the American Chemical Society.

[295]  Takeshi Akasaka,et al.  Location of the metal atoms in Ce2@C78 and its bis-silylated derivative. , 2008, Chemical communications.

[296]  Y. Achiba,et al.  A theoretical approach to C82 and LaC82 , 1993 .

[297]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.

[298]  K. Ohkubo,et al.  Spin-site exchange system constructed from endohedral metallofullerenes and organic donors. , 2006, Journal of the American Chemical Society.

[299]  L. Echegoyen,et al.  Trimetallic nitride endohedral fullerenes: experimental and theoretical evidence for the M3N6+@C2n6- model. , 2009, Angewandte Chemie.

[300]  R. D. Bolskar,et al.  Improved Production and Separation Processes for Gadolinium Metallofullerenes , 2008 .

[301]  Makoto Ohno,et al.  Confirmation by X-ray diffraction of the endohedral nature of the metallofullerene Y@C82 , 1995, Nature.

[302]  S. Nagase,et al.  Two regioisomers of endohedral pyrrolidinodimetallofullerenes M2@I(h)-C80(CH2)2NTrt (M = La, Ce; Trt = trityl): control of metal atom positions by addition positions. , 2009, Chemistry.

[303]  Xing Lu,et al.  Chemistry of endohedral metallofullerenes: the role of metals. , 2011, Chemical communications.

[304]  Steven Stevenson,et al.  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. , 2008, Inorganic chemistry.

[305]  Yuan‐Zhi Tan,et al.  The stabilization of fused-pentagon fullerene molecules. , 2009, Nature chemistry.

[306]  S. Nagase,et al.  Chemical reactivity and redox property of Sc3@C82 , 2004 .

[307]  Shangfeng Yang,et al.  Deviation from the planarity--a large Dy3N cluster encapsulated in an Ih-C80 cage: an X-ray crystallographic and vibrational spectroscopic study. , 2006, Journal of the American Chemical Society.

[308]  L. Echegoyen,et al.  X-Ray crystallographic and EPR spectroscopic characterization of a pyrrolidine adduct of Y3N@C80. , 2006, Chemical communications.

[309]  R. Pan,et al.  Red Emission of Eu(III) Complex Based on 1-(7-(tert-butyl)-9-ethyl-9H-carbazol-2-yl)-4,4,4-trifluorobutane-1,3-dione Excited by Blue Light , 2012 .

[310]  Fred Wudl,et al.  Isolation of the Heterofullerene C59N as Its Dimer (C59N)2 , 1995, Science.

[311]  Xin Lu,et al.  Isolation and characterization of Sc2C2@C68: a metal-carbide endofullerene with a non-IPR carbon cage. , 2006, Angewandte Chemie.

[312]  S. Kawata,et al.  Fourier transform EPR studies of metallofullerene (La@C82) in CS2 solution , 1995 .

[313]  E. Campbell,et al.  Production and LDMS characterisation of endohedral alkalifullerene films , 1997 .

[314]  A. Fujiwara,et al.  Conductivity and field effect transistor of La2@C80 metallofullerene. , 2003, Journal of the American Chemical Society.

[315]  Lothar Dunsch,et al.  Violating the isolated pentagon rule (IPR): the endohedral non-IPR C70 cage of Sc3N@C70. , 2007, Angewandte Chemie.

[316]  Tianming Zuo,et al.  Structure and enhanced reactivity rates of the D5h Sc3N@C80 and Lu3N@C80 metallofullerene isomers: the importance of the pyracylene motif. , 2006, Journal of the American Chemical Society.

[317]  Y. Liu,et al.  The effect of Gd@C82(OH)22 nanoparticles on the release of Th1/Th2 cytokines and induction of TNF-alpha mediated cellular immunity. , 2009, Biomaterials.

[318]  M. Sakata,et al.  An anomalous endohedral structure of Eu@c82 metallofullerenes. , 2005, Angewandte Chemie.

[319]  Zdenek Slanina,et al.  Sc2C2@C80 rather than Sc2@C82: templated formation of unexpected C2v(5)-C80 and temperature-dependent dynamic motion of internal Sc2C2 cluster. , 2011, Journal of the American Chemical Society.

[320]  Kazuya Saito,et al.  Isolation and characterization of the metallofullerene LaC82 , 1993 .

[321]  S. Economopoulos,et al.  Molecular recognition of La@C82 endohedral metallofullerene by an isophthaloyl-bridged porphyrin dimer , 2010 .

[322]  A. Rodríguez‐Fortea,et al.  Understanding the stabilization of metal carbide endohedral fullerenes M2C2@C82 and related systems. , 2008, The journal of physical chemistry. A.

[323]  A. Bartl,et al.  Electron transfer at lanthanum endohedral fullerenes , 1996 .

[324]  S. Fujiki,et al.  Dy@ C60: Evidence for endohedral structure and electron transfer , 2001 .

[325]  P. Fatouros,et al.  Conjugation of functionalized gadolinium metallofullerenes with IL-13 peptides for targeting and imaging glial tumors. , 2011, Nanomedicine.

[326]  S. Nagase,et al.  Synthesis and structural characterization of endohedral pyrrolidinodimetallofullerene: La2@C80(CH2)2NTrt. , 2006, Journal of the American Chemical Society.

[327]  Chunru Wang,et al.  Preparation and ESR study of Sc3C2@C80 bis-addition fulleropyrrolidines. , 2012, Dalton transactions.

[328]  M. Sakata,et al.  High-resolution analysis of (Sc3C2)@ C80 metallofullerene by third generation synchrotron radiation X-ray powder diffraction. , 2006, The journal of physical chemistry. B.

[329]  Xing Lu,et al.  Location of the yttrium atom in Y@C82 and its influence on the reactivity of cage carbons. , 2009, Journal of the American Chemical Society.

[330]  Marilyn M. Olmstead,et al.  A distorted tetrahedral metal oxide cluster inside an icosahedral carbon cage. Synthesis, isolation, and structural characterization of Sc4(mu3-O)2@Ih-C80. , 2008, Journal of the American Chemical Society.

[331]  F. Wudl,et al.  The Higher Fullerenes: Isolation and Characterization of C76, C84, C90, C94, and C70O, an Oxide of D5h-C70 , 1991, Science.

[332]  G. Briggs,et al.  Molecules in carbon nanotubes. , 2005, Accounts of chemical research.

[333]  A. Balch,et al.  Crystallographic characterization of isomer 2 of Er2@C82 and comparison with isomer 1 of Er2@C82. , 2002, Chemical communications.

[334]  Feng Zhu,et al.  Two I(h)-symmetry-breaking C60 isomers stabilized by chlorination. , 2008, Nature Materials.

[335]  J. Larsson,et al.  Modification of the conductance of single fullerene molecules by endohedral doping , 2009 .

[336]  S. Nagase,et al.  Retro-reaction of singly bonded La@C82 derivatives. , 2010, Chemical communications.

[337]  M. Sakata,et al.  Synchrotron Radiation for Structural Chemistry—Endohedral Natures of Metallofullerenes Found by Synchrotron Radiation Powder Method , 2003 .

[338]  A. Bartl,et al.  Pulsed ESR investigations of anisotropic interactions in M@C82 (M=Sc,Y,La) , 1998 .

[339]  K. Ohkubo,et al.  Ion-controlled on-off switch of electron transfer from tetrathiafulvalene calix[4]pyrroles to Li+@C60. , 2011, Journal of the American Chemical Society.

[340]  H. W. Kroto,et al.  The stability of the fullerenes Cn, with n = 24, 28, 32, 36, 50, 60 and 70 , 1987, Nature.

[341]  C. Beavers,et al.  Single samarium atoms in large fullerene cages. Characterization of two isomers of Sm@C92 and four isomers of Sm@C94 with the X-ray crystallographic identification of Sm@C1(42)-C92, Sm@C(s)(24)-C92, and Sm@C3v(134)-C94. , 2012, Journal of the American Chemical Society.

[342]  J. Alford,et al.  Chemical redox recovery of giant, small-gap and other fullerenes , 2011 .

[343]  B. Holloway,et al.  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. , 2008, Chemical communications.

[344]  A. Rodríguez‐Fortea,et al.  The maximum pentagon separation rule provides a guideline for the structures of endohedral metallofullerenes. , 2010, Nature chemistry.

[345]  S. Nagase,et al.  A singly bonded derivative of endohedral metallofullerene: La@C82CBr(COOC2H5). , 2005, Journal of the American Chemical Society.

[346]  D. Guldi,et al.  Utilization of Sc3N@C80 in long-range charge transfer reactions. , 2011, Chemical communications.

[347]  Jiechao Ge,et al.  Gd2@C79N: isolation, characterization, and monoadduct formation of a very stable heterofullerene with a magnetic spin state of S = 15/2. , 2011, Journal of the American Chemical Society.

[348]  S. Nagase,et al.  Theoretical study of the dimetallofullerene Sc2@C84 , 1994 .

[349]  Xing Lu,et al.  Nitrated benzyne derivatives of La@C(82): addition of NO(2) and its positional directing effect on the subsequent addition of benzynes. , 2010, Angewandte Chemie.

[350]  Edward Van Keuren,et al.  Endohedral fullerenes for organic photovoltaic devices. , 2009, Nature materials.

[351]  Q. Kong,et al.  Formation of various types of metallofullerenes by laser ablation of externally doped fullerenes C60Mx (M=Sm, Pt, Ni, La, Y, and Rh) , 2002 .

[352]  J. Campanera,et al.  General rule for the stabilization of fullerene cages encapsulating trimetallic nitride templates. , 2005, Angewandte Chemie.

[353]  Wujun Fu,et al.  Highly regioselective derivatization of trimetallic nitride templated endohedral metallofullerenes via a facile photochemical reaction. , 2008, Journal of the American Chemical Society.

[354]  S. Nagase,et al.  A co-crystal composed of the paramagnetic endohedral metallofullerene La@C82 and a nickel porphyrin with high electron mobility. , 2012, Angewandte Chemie.

[355]  Shangfeng Yang,et al.  The cycloaddition reaction of I(h)-Sc₃N@C₈₀ with 2-amino-4,5-diisopropoxybenzoic acid and isoamyl nitrite to produce an open-cage metallofullerene. , 2011, Angewandte Chemie.

[356]  W. Klopper,et al.  Switchable open-cage fullerene for water encapsulation. , 2010, Angewandte Chemie.

[357]  Y. Murata,et al.  A Single Molecule of Water Encapsulated in Fullerene C60 , 2011, Science.

[358]  Takeshi Akasaka,et al.  Endohedral metal atoms in pristine and functionalized fullerene cages. , 2010, Accounts of chemical research.

[359]  Keith E. Whitener,et al.  Putting ammonia into a chemically opened fullerene. , 2008, Journal of the American Chemical Society.

[360]  E. Zhang,et al.  Size effect of encaged clusters on the exohedral chemistry of endohedral fullerenes: a case study on the pyrrolidino reaction of ScxGd3-xN@C80 (x = 0-3). , 2007, Organic letters.

[361]  Electron spin relaxation of N@C60 in CS2 in CS2. , 2005, The Journal of chemical physics.