Abstract
New quinoidal fused oligosiloles containing an even number of silole units have been synthesized by a rhodium-catalyzed stitching reaction. Employing [RhCl(tfb)]2 as the catalyst significantly improved the stitching efficiency, and up to six siloles could be fused in quinoidal form. A systematic comparison of the physical properties of Si1-Si6' confirmed the unique trend in their LUMO levels, which become higher with longer π conjugation. To understand the origin of this unusual trend, theoretical calculations were also carried out using various model compounds, and the results indicated that the terminal indenylidene (cyclopentadienylidene) moieties in Si1-Si6 (Si1a-Si6a) are primarily responsible for this phenomenon through their frontier orbital correlations with the HOMO of the central polyene unit, which becomes higher in energy with longer π conjugation.
Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
