1, ω-Bis [8-(dimethylamino)-1-naphthyl]-1, ω-difluorotrisilane 1 (ω= 3) and tetrasilane 2 (ω= 4) have been prepared. The X-ray crystallography of dl-1 and meso-1 shows unsymmetrical structures having different coordination modes at the two terminal silicons. The unsymmetrical nature of the structure of 1 can also be observed by solid state CP/MAS NMR spectroscopy. Trisilane 1 is thermochemically labile and undergoes facile degradation at ...