Endohedral Metallofullerenes

Hisanori Shinohara Department of Chemistry, Nagoya University, JapanNikos Tagmatarchis Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, GreeceForeword by Sir Harold Kroto

• Foreword ix Preface xiPersonal Reflection – Nori Shinohara xiii1 Introduction 11.1 The First Experimental Evidence of Metallofullerenes 11.2 Early Years of Metallofullerene Research 31.3 Conventional and IUPAC Nomenclature for Metallofullerenes 5References 62 Synthesis, Extraction, and Purification 92.1 Synthesis of Endohedral Metallofullerenes 92.2 Solvent Extraction of Metallofullerenes from Primary Soot 142.3 Purification and Isolation by HPLC 152.4 Fast Separation and Purification with Lewis Acids 18References 193 Molecular and Crystal Structures 233.1 Endohedral or Exohedral? A Big Controversy 233.2 Structural Analyses 25References 374 Electronic States and Structures 434.1 Electron Transfer in Metallofullerenes 434.2 ESR Evidence on the Existence of Structural Isomers 454.3 Electrochemistry of Metallofullerenes 484.4 Similarity in the UV]Vis]NIR Absorption Spectra 514.5 Fermi Levels and the Electronic Structures 574.6 Metal–Cage Vibration within Metallofullerenes 59References 635 Carbide and Nitride Metallofullerenes 695.1 Discovery of Carbide Metallofullerenes 695.2 Fullerene Quantum Gyroscope: An Ideal Molecular Rotor 755.3 Nitride Metallofullerenes 77References 816 Non]Isolated Pentagon Rule Metallofullerenes 856.1 Isolated Pentagon Rule 856.2 Non]IPR Metallofullerenes 86References 897 Oxide and Sulfide Metallofullerenes 917.1 O xide Metallofullerenes 917.2 Sulfide Metallofullerenes 95References 1008 Non]metal Endohedral Fullerenes 1038.1 Nitrogen]Containing N@C60 1038.2 Phosphorus]Containing P@C60 1118.3 Inert Gas Endohedral Fullerenes He@C60, Ne@C60, Ar@C60, Kr@C60, and Xe@C60 1128.4 Hydrogen]Containing H2@C60 1208.5 Water]Containing H2O@C60 125References 1289 Scanning Tunneling Microscopy Studies of Metallofullerenes 1339.1 STM Studies of Metallofullerenes on Clean Surfaces 1339.2 Metallofullerenes as Superatom 1359.3 STM/STS Studies on Metallofullerene Layers 1379.4 STM/STS Studies on a Single Metallofullerene Molecule 139References 14110 Magnetic Properties of Metallofullerenes 14510.1 Magnetism of Mono]metallofullerenes 14510.2 SXAS and SXMCD Studies of Metallofullerenes 149References 15411 Organic Chemistry of Metallofullerenes 15711.1 Cycloaddition Reactions 15711.2 Radical Addition Reactions 17811.3 Miscellaneous Reactions 18011.4 Donor–Acceptor Dyads 18511.5 Bis]adduct Formation 19411.6 Supramolecular Functionalization 19511.7 Purification of Metallofullerenes by Chemical Methods 198References 20012 Applications with Metallofullerenes 20912.1 Solar Cells 20912.2 Biomedical Aspects of Water]Soluble Metallofullerenes 221References 22613 Growth Mechanism 22913.1 Carbon Clusters: A Road to Fullerene Growth 22913.2 Roles Played by Metal Atoms in the Fullerene Growth 23313.3 Top]Down or Bottom]Up Growth? 237References 25114 M@C60: A Big Mystery and a Big Challenge 25514.1 What Happens to M@C60? 25514.2 A Big Challenge: Superconductive Metallofullerenes 25914.3 Future Prospects 261References 262Index 265