Camouflaged carborarods derived from B-permethyl-1,12-diethynyl-para- and B-octamethyl-1,7-diethylnyl-meta-carborane modules

Rigid camouflaged carborarods constructed from the corresponding C,C'-diethynyl derivatives of B-decamethyl-1,12-dicarbadodecaborane(12) (6) and B-octamethyl-1,7-dicarbadodecaborane(12) (48) have been synthesized by largely conventional organic transformations. These carborarods are the longest discrete rod species available by this method in which B-methylated p-carborane and m-carborane cages are linked through their carbon vertices by using butadiynylene moieties. They exhibit enhanced solubility in common organic solvents relative to all other presently known carborane-based rigid-rod molecules. The oxidative coupling of bis(ethynyl) derivatives of 6 generates oligomers containing, on average, 16 carborane modules. The structural characterization of the corresponding dimeric species revealed that the carborarods possess a sinusoidal chain distortion in the solid state. The stereoelectronic properties of these and related model carborarods were evaluated by using molecular dimensions as a monitor for the comparison of computational and experimental methods. In addition, the effect of exhaustive B-methylation of 12- and 10-vertex para-carborane cages in a series of model C,C'-diethynyl derivatives was similarly investigated by computational and structural studies. As expected, a correlation of intercage C--C bond lengths with cage size was observed and was attributed to hybridization effects. B-Permethylation had no significant structural effect with either 10- or 12-vertex cage derivatives. Relative to unsubstituted compounds, thermal and chemical stabilities of B-permethylated derivatives were increased through the operation of a steric "bumper-car" process, and solubilities in organic solvents were enhanced. The formation of linear, sterically encumbered platina-carborarods using ethynyl derivatives of 6 as precursors is described.