Coplanar Oligo(p-phenylenedisilenylene)s as Si═Si Analogues of Oligo(p-phenylenevinylene)s: Evidence for Extended π-Conjugation through the Carbon and Silicon π-Frameworks

A series of oligo(p-phenylenedisilenylene)s (Si-OPVs 1-4), silicon analogues of oligo(p-phenylenevinylene)s, up to the tetramer have been synthesized and isolated by the introduction of a newly developed protecting group [(HexO)MEind] for improving their solubility. The experimental and theoretical studies of the Si-OPVs 1-4 demonstrate the fully extended π-conjugation of the Si-OPV main chains. Single crystal X-ray analyses of the monomer 1 and the dimer 2 revealed the highly coplanar Si-OPV backbones facilitating the effective extension of the π-conjugation, which has further been validated by the significant increases in the absorption maxima from 465 nm for the monomer 1 to 610 nm for the tetramer 4. The absorption maxima exhibit an excellent fit to Meier's equation, leading to the estimation of an effective conjugation length (ECL) of 9 repeat units (nECL = 9) and the absorption maximum of 635 nm for the infinite chain (λ∞ = 635 nm). In sharp contrast to other nonemissive disilenes, the Si-OPVs 2-4 show an intense fluorescence from 613 to 668 nm at room temperature with the quantum yields up to 0.48. All the data presented here provide the first evidence for the efficient extended π-conjugation between the Si═Si double bonds and the carbon π-electron systems over the entire Si-OPV skeleton. This study reveals the possibility for developing the conjugated disilene π-systems, in which the Si═Si double bonds would be promising building blocks, significantly optimizing the intrinsic photophysical and electrochemical properties of the carbon-based π-conjugated materials.