Carboranes as guests, counterions and linkers in coordination polymers and networks

•Carborane clusters as building blocks in coordination polymers.•1D-coordination polymers and 2D- and 3D-networks.•Functionalization of carborane clusters with carboxylato, phosphino, thiolato or 2,2′:6′,2″-terpyridinyl domains.•Carborane clusters captured as guest molecules.•Carboranes as weakly coordinating anions.

Carborane clusters play a variety of roles in the assembly of 1D-coordination polymers and 2D- and 3D-networks. In this review, comments on coordination polymers in which neutral carborane guests are accommodated are followed by discussion of the incorporation of anionic carboranes into coordination polymers and networks, with critical comments concerning the classification of some ‘coordination polymers’ within the 2013 IUPAC guidelines. Functionalization of carborane clusters with carboxylato, phosphino, thiolato or 2,2′:6′,2″-terpyridinyl domains provides potential for their incorporation as covalently bound linkers into the backbones of coordination polymers and frameworks; in the case of phosphino- and thiolato-functionalized clusters, the carborane clusters are located on the periphery of the 1D-polymer chains.

Graphical abstractThis review demonstrates the variety of ways in which carborane clusters have been used in the assembly of 1D-coordination polymers, and 2D- and 3D-networks, either as guests, counterions or peripheral groups, or as building blocks within the framework of the assembly.Figure optionsDownload full-size imageDownload as PowerPoint slide