Since their first detection and bulk production, the fullerenes have
gained a primary role on the scientific scene, reaching their climax when
the 1996 Nobel Prize for Chemistry was awarded to Kroto, Curl and Smalley
for their seminal discovery. The unique physical and chemical properties
of these new forms of carbon led many scientists to predict several
technological applications. This created a heavy disappointment when it
was clear that fullerene-based materials would not soon be ready for the
market. However, the fullerenes have so far delighted several dozens of
researchers who found that C
 60
 and its relatives undergo a
variety of chemical reactions. In most cases, the new derivatives retain
the main properties of the original fullerene, and it is now not unlikely
that some functionalized fullerenes may find useful applications in the
field of materials science and technology. In this Article we summarize
the basic principles of the organic chemistry of fullerenes, together with
a description of the physicochemical properties that have made these
carbon cages popular in materials science, and review the most recent
achievements in the functionalization of fullerenes aimed at the
production of new molecular materials.

[60]Fullerene chemistry for materials science applications

The covalent functionalization of C 60 has developed vigorously over the past 5 years. Several methods are now available for the formation of C 60 monoadducts. Regioselective formation of multiple adducts has allowed study of the changes in chemical and physical properties that occur when the conjugated fullerene chromophore is reduced during an increase in functionalization. The systematic development of covalent fullerene chemistry provides an unprecedented diversity of tailor-made three-dimensional building blocks for technologically interesting materials.

http://science.sciencemag.org/content/sci/271/5247/317.full.pdf

Covalent Fullerene Chemistry

The discovery and large-scale synthesis of fullerenes have aroused interdisciplinary interest in these closed-cage molecules1,2,3,4,5,6 C60 can be photopolymerized into a form in which the cages are thought to be linked by cyclic C4 units in a [2 + 2] cycloaddition7, provoking theoretical studies of the C60 dimer8,9,10,11,12,13,14,15, the smallest subunit of such a polymer The C60 dimers C120O (refs 16, 17), C121H2( ref 17) and C120O2(ref 18) have been reported, in which the two C60molecules are linked by, respectively, a furan group, a cyclopentane ring and a cyclobutane ring plus two oxygen bridges; but the simplest dimer, C120linked by a cyclobutane ring alone, has not so far been observed We now report that this dumb-bell-shaped molecule can be synthesized by a solid-state mechanochemical reaction of C60 with potassium cyanide Our X-ray structural analysis shows that the C4 ring connecting the cages is square rather than rectangular—the latter is predicted theoretically8,9,13,14,15 The dimer dissociates cleanly into two C60 molecules on heating or one-electron reduction, but in the gas phase during mass-spectrometric measurements it undergoes successive loss of C2 units, shrinking to even-numbered fullerenes such as C118 and C116 in a sequence similar to that seen for other large fullerenes19,20

/pdf/synthesis-and-x-ray-structure-of-dumb-bell-shaped-c-120-13launlzy5.pdf

Synthesis and X-ray structure of dumb-bell-shaped C 120

A. Lanthanum, Yttrium, and Scandium 2126 B. Hafnium, Zirconium, and Titanium 2126 C. Tantalum, Niobium, and Vanadium 2127 D. Tungsten, Molybdenum, and Chromium 2127 E. Rhenium, Technetium, and Manganese 2128 F. Osmium, Ruthenium, and Iron 2128 1. Osmylation 2128 2. Reactions with Zerovalent Compounds 2131 3. Other Addition Reactions 2133 4. Redox Reactions 2134 5. Cocrystallizations 2134 G. Iridium, Rhodium, and Cobalt 2135 1. Adduct Formation with Vaska-Type Complexes, Ir(CO)Cl(PR3)2 2135

/pdf/reactions-of-transition-metal-complexes-with-fullerenes-c60-1hra1tblh6.pdf

Reactions of transition metal complexes with fullerenes (c60, c70, etc.) and related materials

Structural aspects of fullerene chemistry--a journey through fullerene chirality.

Synthesis of C120O: A new dimeric [60]fullerene derivative

Hydrogenation of buckminsterfullerene C60 via Hydrozirconation: A new way to organofullerenes

C120O2: The first [60]fullerene dimer withcages bis-linked by furanoid bridges

The reaction of the C60 hydrozirconation adduct 1 with N-bromosuccinimide and m-chloroperbenzoic acid leads to the formation of Diels–Alder products with bromo- and hydroxy-cyclopentadiene, respectively.

Unusual functionalization of C60via hydrozirconation: reactivity of the C60–ZrIV complex vs. alkyl–ZrIV complexes

Chemistry at cyclopentene addends on [60]fullerene. Matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF MS) as a quick and facile method for the characterization of fullerene derivatives

Stephan Ballenweg

Papers

Synthesis of C120O: A new dimeric [60]fullerene derivative

Hydrogenation of buckminsterfullerene C60 via Hydrozirconation: A new way to organofullerenes

C120O2: The first [60]fullerene dimer withcages bis-linked by furanoid bridges

Unusual functionalization of C60via hydrozirconation: reactivity of the C60–ZrIV complex vs. alkyl–ZrIV complexes

Chemistry at cyclopentene addends on [60]fullerene. Matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF MS) as a quick and facile method for the characterization of fullerene derivatives