NONMOLECULAR METAL CHALCOGENIDE HALIDE SOLIDS AND THEIR MOLECULAR CLUSTER ANALOGS

A variety of transition‐metal cluster structures are found within the extended arrays of solidstate materials. Although molecular analogues of some of these clusters have been synthesized—either by the self‐assembly of smaller components in solution or by the excision of intact cluster units directly from the solid‐state phase—molecular chemists are often unaware of the rich structural variety expressed in solid‐state clusters. This article presents these diverse structural types as potential targets for synthetic molecular chemistry by describing fundamental solid‐state cluster topologies in transition‐metal chalcogenide/halide phases and detailing cases where molecular counterparts have been prepared. Particular emphasis is placed on cluster excision as a method of molecular cluster synthesis. Copyright © 1990 by VCH Verlagsgesellschaft mbH, Germany