Polyfluorene-based conjugated nanocomposites with in-situ gold nanoparticles: Synthesis via rational chemical passivation and characterization of supramolecular fibrillar structures

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We present a rational and innovative chemical approach for synthesizing and characterizing conjugated polymer nanocomposites as direct passivation of gold nanoparticles (AuNPs), highlighting intrinsic morphologies and distinct photophysical properties in the solid state. The pioneering synthesis of polyfluorene with thiol, LaPPS79.10, revolutionized its application as a direct passivator of AuNPs, resulting in stable nanocomposites with the capacity for storage in the dry state and subsequent redispersion in organic solvent. The presence of AuNPs with average diameters of 3.5 ± 1.3 nm induced the formation of an interconnected fibrillar supramolecular network (ribbon-like) and several microdomains in the nanocomposite (LaPPS79.10+AuNPs), correlated by XRD, TEM and SEM measurements. Characterization of the polyfluorene precursor derivative, LaPPS10, revealed bundle-like morphologies with aggregation-induced emission (AIE). Introducing thiol groups into the intermediate structure induced polymer chain organization (LaPPS79.10), leading to unique straw-like and lenticular bundle morphologies, disrupting the non-planar π-π packing and quenching the emission, a case of aggregation-caused quenching (ACQ). In LaPPS79.10+AuNPs, the proximity of the π system to the Au localized surface plasmon resonance (LSPR) resulted in high absorption, negligible self-absorption, and efficient emission quenching, as well as improved thermal resistance compared to the original polymer. The unprecedented discovery of the properties resulting from the electronic interaction between the π system of the AuNPs passivating polymer and the effects of plasmonic resonance represents a significant advance in nanoscience, opening new perspectives for exciting applications in organic photovoltaic devices and metamaterials.