A selective review on the making of coordination networks with potential semiconductive properties

This paper provides a concise review of some recent developments in the synthesis and preparation of crystalline coordination networks with potential semiconductive properties. The scope is selective rather than inclusive, with special emphasis on representative compounds exhibiting generic features that could enhance electronic coupling between the metal center and the ligand π-systems, and, as a result, could point to general methods of forming semiconductive networks. The majority of systems selected herein are based on direct bonding interactions between the metal centers and polycyclic aromatic hydrocarbon (PAH) units, highlighting the importance of this class of organic molecules in the making of crystalline electronic materials. Besides the extensive efforts in ligand synthesis, new dimensions for accessing novel semiconductive systems are also derived from the design and choice of the metal center species, including simple ions (e.g., Ag⁺), metal halide components (e.g., BiCl₃ and BiBr₃) and the more recently developed Lewis acid linkers with multiple binding sites [e.g., dirhodium(II) tetracarboxylate]. © 2006 Elsevier B.V. All rights reserved.