π-Conjugated species with an unsupported Si-Si π-bond obtained from direct π-extension.

1,3-Diethynylbicyclo[1.1.0]tetrasilanes that contain an unsupported bridgehead Si-Si π-bond and ethynyl π-moieties were synthesized by the reaction of a 1,3-dihalobicyclo[1.1.0]tetrasilane with the corresponding lithium acetylide. The substantial bathochromic shift of the longest-wavelength absorption band observed for the phenylethynyl-substituted bicyclo[1.1.0]tetrasilane in the solid state compared to that of the octynyl-substituted derivative suggested the presence of effective π-conjugation between the unsupported Si-Si π and ethynyl π units.