Abstract
Reaction of a 2,5-dilithiated silole with excess dichlorodimethylsilane gives the respective 2,5-bis(chlorodimethylsilyl) substituted silole. This compound can be converted to 2,5-bis(oligosilanyl) substituted siloles by addition of a suitable oligosilanide. In the UV spectra of the thus obtained compounds the lowest energy absorptions are bathochromically shifted compared to the absorptions of the two constituents, namely the 2,5-disilyl substituted silole and a trisilane. The bathochromic shift is interpreted as being caused by a mixed σ-conjugation/cross-hyperconjugation. This assumption is supported by TD-DFT calculations, which show a significant contribution from Si-Si bonds to the HOMO of the molecule.