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Nanoscale Atoms in Solid-State Chemistry

Science  12 Jul 2013:
Vol. 341, Issue 6142, pp. 157-160
DOI: 10.1126/science.1236259

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Ionic Materials via Charged Clusters

The formation of salts from atomic and small molecular ions could in principle be replicated with larger inorganic clusters. However, many clusters are stabilized by organic ligands that create a barrier for charge transfer reactions to create ions. Roy et al. (p. 157, published online 6 June; see the Perspective by Batail) now report that chromium, cobalt, and nickel selenide and telluride clusters form materials by charge transfer with C60. The Co and Cr clusters formed a layered structure analogous to CdI2, while the Ni cluster formed a structure related to NaCl.

Abstract

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.

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