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We describe a solid-state material formed from binary assembly of atomically precise molecular clusters. [Co6Se8(PEt3)6][C60]2 and [Cr6Te8(PEt3)6][C60]2 assembled into a superatomic relative of the cadmium iodide (CdI2) structure type. These solid-state materials showed activated electronic transport with activation energies of 100 to 150 millielectron volts. The more reducing cluster Ni9Te6(PEt3)8 transferred more charge to the fullerene and formed a rock-salt-related structure. In this material, the constituent clusters are able to interact electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.

CHCl3 and CHBr3 intercalated C60 have attracted particular interest after a superconductivity transition temperature (Tc) of up to 117 K was discovered. We have determined the structure using synchrotron x-ray powder-diffraction and found that the expansion of the lattice mainly takes place in one dimension (triclinic b axis), leaving planes of C60 molecules on an approximately hexagonal, slightly expanded lattice. We have performed tight-binding band structure calculations for the surface layer. In spite of the slight expansion of the layers, for the range of dopings where a large Tc has been observed, the density of states at the Fermi energy is smaller for C60.2CHCl3 and C60.2CHBr3 than for C60. This suggests that the lattice expansion alone cannot explain the increase of Tc.