Hyperbranched Conjugated Polysiloles: Synthesis, Structure, Aggregation-Enhanced Emission, Multicolor Fluorescent Photopatterning, and Superamplified Detection of Explosives

Hyperbranched poly(2,5-silole)s [hb-P1(m), m = 1, 6] are synthesized for the first time in this work. 1,1-Dialkyl-2,5-bis(4-ethynylphenyl)-3,4- diphenylsiloles [1(m)] were polymerized by TaBr₅, affording hb-P1(m) with high molecular weights (M_w up to 2.5 × 10⁵) in high yields (up to 98%). The structures of hb-P1(m) were characterized by spectroscopic methods and the degree of branching of hb-P1(6) was determined to be 0.55. The hyperbranched polymers are soluble and stable, with no changes in solubility observed after they have been stored under ambient conditions for more than two years. Absorption and emission spectra of hb-P1(m) are red-shifted from those of 1(m), indicating that the polymers are more conjugated than the monomers. Both 1(m) and hb-P1(m) are nonemissive or weekly fluorescent when dissolved in their good solvents but become highly emissive when aggregated in their poor solvents or fabricated into thin solid films, showing unusual phenomena of aggregation-induced (AIE) and -enhanced emissions (AEE). Restriction of intramolecular rotations in the aggregate state is rationalized to be the main cause for the AIE and AEE effects. Photoluminescence (PL) of 1(m) and hb-P1(m) is tunable by varying their concentrations and morphologies. The polymers are readily cured when heated to high temperatures or upon photoirradiation, furnishing cross-linked networks with novel excitation wavelength-dependent emissions in the red spectral region. Photolithography of hb-P1(m) generates fluorescent photopatterns, with the exposed and unexposed areas emitting lights with different colors. The polymers function as sensitive fluorescent chemosensors for the detection of explosives, with a superamplification effect observed in the emission quenching of the polymer nanoaggregates by picric acid.