High Fluorescence Quantum Yield Based on the Through-Space Conjugation of Hyperbranched Polysiloxane

Unorthodox luminogenic polymers without aromatic luminogens have attracted great interest in recent years; however, the low fluorescence efficiency is still a big drawback. In this paper, we synthesized a fluorescent hyperbranched polysiloxane with both carbonyl and vinyl groups (P1). Surprisingly, it exhibited nontraditional intrinsic luminescence with the highest quantum yield up to 43.9% among the reported silica-containing hyperbranched fluorescent polymers to date. Reference oligomers P2 and P3, theoretical calculations, and transmission electron microscopy were employed to explore the fluorescence mechanism. The high fluorescence quantum yield is ascribed to the synergism of vinyl and carbonyl groups as well as the Si-O group-promoted through-space conjugation. Thus, the supramolecular hyperbranched polysiloxane was assembled by conjugation to increase the oscillator strength and decrease the band gap. Moreover, the solvent effect and pH dependency properties of P1 and its application as an Fe ³⁺ probe were also studied.