Synthesis, Light Emission, Nanoaggregation, and Restricted Intramolecular Rotation of 1,1-Substituted 2,3,4,5-Tetraphenylsiloles

TLDR: A series of 10 2,3,4,5-tetraphenylsiloles with different 1,1-substituents [XYSi(CPh)4] were prepared, and three of them were characterized crystallographically as mentioned in this paper.

Abstract: A series of ten 2,3,4,5-tetraphenylsiloles with different 1,1-substituents [XYSi(CPh)4] were prepared, and three of these, i.e., 1,1,2,3,4,5-hexaphenylsilole [X = Y = Ph (3)], 1-ethynyl-1,2,3,4,5-pentaphenylsilole [X = Ph, Y = C⋮CH (15)], and 1,1-bis(phenylethynyl)-2,3,4,5-tetraphenylsilole [X = Y = C⋮CPh (18)], were characterized crystallographically. The ground- and excited-states of the siloles were influenced by the inductive effect of the 1,1-substituents:  with an increase in their electronegativity, the absorption and emission spectra of the siloles bathochromically shifted. A simple and reliable TLC-based method was developed for measurement of the solid-state luminescence spectra of the siloles. When molecularly dissolved in common solvents at room temperature, all the siloles were practically nonemissive (“off”). When poor solvents were added, the silole molecules clustered into nanoaggregates, which turned the emission “on” and boosted the photoluminescence quantum yields by up to 2 orders of m...