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

Abstract

review is dedicated to Russ Grimes, a true pioneer in carborane (carborane) cluster chemistry, on the occasion of his 80th birthday. AbstractCarborane 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 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-functionalized clusters, the carborane clusters are located on the periphery of the 1D-polymer chains.

Icosahedral boron clusters: a perfect tool for the enhancement of polymer features

“…19). 43 The incorporation of carborane clusters as linkers in coordination polymers can be realized by introducing the metalbinding group directly bonded to the cage. The HÁ Á ÁAg distance of 2.17 Å is shorter than distances observed in other silver polymers containing the (1) anion.…”

Silver and Copper Complexes with closo-Polyhedral Borane, Carborane and Metallacarborane Anions: Synthesis and X-ray Structure

“…Therefore, synthesis and X-ray structure studies of silver and copper salts of new types of weakly coordinating anions are of great importance. Several review papers concerning different aspects of chemistry of silver and copper complexes of polyhedral boranes and carboranes were published during the recent years [12][13][14].…”

A Microporous Metal‐Organic Framework Supramolecularly Assembled from a CuII Dodecaborate Cluster Complex for Selective Gas Separation

“…[13] Thec age size defined by the distance between opposite hydrogen atoms is about 5.6 .T he salt [Et 3 NH] 2 [B 12 H 12 ]c an be easily prepared on a2 5g scale by ao ne-pot synthesis from commercially available reagents. Neutral carboranes C 2 B 10 H 12 , [14] as relatives of [B 12 H 12 ] 2À , have been utilized as unique building blocks for MOFs after linking them through pyridyl or carboxy groups,w hich serve as the coordinating moieties.T hese MOFs have unique physical and chemical properties that are distinct from those of normal MOFs with purely organic ligands. [15] However, as ac onsequence of the limited number of methods to selectively functionalize [B 12 H 12 ] 2À as well as the potential disadvantage of its weakly coordinating nature,the construction and applications of MOFs using [B 12 H 12 ] 2À have not yet been reported.…”