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 TaX 5 −Ph 4 Sn (X = Cl, Br) and CpCo(CO) 2 − h ν catalysts, yielding soluble hyperbranched polyarylenes ( hb -PAs) with high molecular weights ( M w up to ∼1.6 × 10 5 ) 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 ( T d up to 560 °C) with high weight residues ( W r 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 Φ F 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.