Synthesis, Thermal Stability, and Linear and Nonlinear Optical Properties of Hyperbranched Polyarylenes Containing Carbazole and/or Fluorene Moieties

New diyne monomers containing carbazolyl and/or fluorenyl chromophores, namely, 3,6-diethynyl-9-phenylcarbazole (1), 3,6-diethynyl-9-[6-(9-carbazolyl)hexyl]carbazole (2), and 2,7-diethynyl-9,9-bis[6-(9-carbazoyl)hexyl]fluorene (3), are synthesized. Alkyne polycyclotrimerizations are effected by TaX5−Ph4Sn (X = Cl, Br) and CpCo(CO)2−hν catalysts, yielding soluble hyperbranched polyarylenes (hb-PAs) with high molecular weights (Mw up to ∼1.6 × 105) in high yields (up to ∼100%). The structures and properties of the hb-PAs are characterized and evaluated by IR, NMR, UV, PL, TGA, and optical limiting analyses. Most of the hb-PAs show outstanding thermal stability (Td up to 560 °C) with high weight residues (Wr up to ∼86%) after pyrolysis at 800 °C. Upon photoexcitation, solutions of the hb-PAs emit strong blue light of ∼400 nm with fluorescence quantum yields ΦF up to 90%. The hb-PAs show excellent optical limiting performance and strongly attenuate the powder of 8 ns pulses of 532 nm laser light.