The review generalises for the first time the published data on the synthesis and properties of donor-acceptor type of compounds based on fullerenes, various solvates and clathrates, inclusion compounds, molecular complexes and charge-transfer complexes both with inorganic donors and with organoelement donors of the tetrathiafulvalene, amine, metallocene and metalloporphyrin series. Radical ionic salts of fullerenes with bulky cations and alkali metals obtained by intercalation or by direct synthesis in solution are discussed. Results of studies of fullerene compounds by IR, optical, ESR, X-ray photoelectron and 13C NMR spectroscopy, as well as their conducting (including superconducting), magnetic and optical properties are discussed. The bibliography includes 208 references.

Donor?acceptor complexes and radical ionic salts based on fullerenes

To improve the understanding of the solution properties of C60 and C70 in aromatic solvents, binary systems of C60 and C70 with benzene, toluene, 1,2- and 1,3-dimethylbenzene, 1,2,4- and 1,3,5-trimethylbenzene, bromobenzene, and 1,2- and 1,3-dichlorobenzene were studied using differential scanning calorimetry, solution calorimetry, and thermogravimetry. Solid solvates with different compositions were identified in many of the systems. The solvates were characterized by composition and by the temperature and the enthalpy of the incongruent melting transition. Enthalpies of solution of C60 in toluene, 1,2-dimethylbenzene, 1,2- and 1,3-dichlorobenzene, and 1,2,4-trimethylbenzene and of C70 in 1,2-dimethylbenzene and in 1,2- and 1,3-dichlorobenzene were determined. The formation−incongruent melting of solid solvates causes maxima in the temperature−solubility curves of fullerenes in aromatic solvents. Trends in solubility behavior of fullerenes were discussed in terms of thermodynamics of solution and solvate...

Calorimetric Studies of Solvates of C60 and C70 with Aromatic Solvents

Differential scanning calorimetry, solution calorimetry, and room-temperature single-crystal X-ray diffraction were used to study the thermodynamic and structural properties of a solvated crystal C60·2C6H5Br. In the monoclinic solvate, two orientations of C60 were observed with fractional populations of 0.71 and 0.29. The enthalpy of solution of pure C60 in bromobenzene was determined to be ΔsolH[C60(s)] = −11.5 ± 2.0 kJ/mol. The enthalpy of solution of the solvated crystal was ΔsolH[C60·2C6H5Br(s)] = +28 ± 1 kJ/mol. The phase diagram of the system C60−C6H5Br for T < 423 K was constructed. It predicts the existence of a maximum in the temperature−solubility relationship for C60 in bromobenzene at 350 K. The activity of bromobenzene vapor over the solvated crystal is predicted to be reduced from its value over the pure liquid by a factor of 3.5.

C60·Bromobenzene Solvate: Crystallographic and Thermochemical Studies and Their Relationship to C60 Solubility in Bromobenzene

By slowly evaporating solutions of fullerene ${\mathrm{C}}_{60}$ in 1,2-dichloroethane at room temperature, crystals of an orthorhombic 1:1 solvate are obtained [$Cmcm,$ ${\mathrm{Cmc}2}_{1},$ or $\mathrm{Ama}2,$ with $a=10.065(9)\AA{},$ $b=31.34(3)\AA{},$ and $c=10.059(8)\AA{}$ ($C$ setting)]. Unusual decagonal needles with dihedral angles of $\ensuremath{\sim}36\ifmmode^\circ\else\textdegree\fi{}$ between adjacent faces also form. They are described in terms of a $10\ifmmode\times\else\texttimes\fi{}$ twinning of these orthorhombic crystals with needle axis (or twin axis [001]) parallel to composition planes in the form ${1K0}$ whose orientations do not correspond to rational index $k (9lKl10).$ This solvate decomposes with a desolvation enthalpy (45 kJ per mole of solvent) close to that of sublimation for pure solvent and it forms with a negative excess volume ($\ensuremath{-}23{\AA{}}^{3}$ per formula unit). Despite a packing coefficient (0.77) higher than that for hard sphere close packing (0.74), it spontaneously decomposes at room temperature. This is related to the solvent adsorption on cubic ${\mathrm{C}}_{60}$ which is shown to be preferred to the solvate formation by about $\ensuremath{-}10\mathrm{kJ}$ per mole of solvent.

Solid-state studies on single and decagonal crystals of C 60 grown from 1,2-dichloroethane

Stable van der Waals-bonded C60/benzene solvates were prepared using a novel crystallization technique. Solid-state NMR measurements on highly crystalline solvate under liquid benzene show that there is very little interaction between benzene and the C60 molecules and that the rotation of C60 at room temperature is not hindered. The magnetization transfer between benzene protons and local C60 molecules is highly inefficient. Three benzene species have been found in the solvate:  two, nearly freely mobile, in wide and narrow porous structures, and the third constrained by C60 molecules in lattice defects. Premelting of deuterated benzene within the C60 solvate has been observed at Tm − 10.5 K.

Solid-State NMR Studies of Fullerene C60/Benzene Solvates

Solid-state studies on C60 solvates grown from n-heptane

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Solid-state studies on C60 solvates grown from n-heptane