Structures and Physical Properties of Chemically Reduced Diindenosiloles and Their π‑Extended Derivatives

Diindenosilole Si1, a silicon-bridged fulvalene derivative, was successfully reduced to its dianions using various alkali metals, and the structures were characterized by X-ray crystallographic analysis. Radical anions of Si1 as well as dianions of π-extended Si3 could also be synthesized, and the structural and physical properties were systematically compared. It was also found that the NMR spectra of dianions Si12– and Si32– show countercation and temperature dependency for their signal broadness, indicating the possible existence of thermal interconversion between closed-shell singlet states and open-shell triplet states.