Synthesis and properties of helical polyacetylenes containing carbazole

Abstract

Novel acetylene monomers containing carbazole with chiral menthyl and bornyl groups, 9-(1 R,2 S,5 R)-menthyloxycarbonyl-2-ethynylcarbazole ( 1), 9-(1 S,2 R,5 S)-menthyloxycarbonyl-2-ethynylcarbazole ( 2), 9-(1 R,2 S,5 R)-menthyloxycarbonyl-3-ethynylcarbazole ( 3) and 9-(1 S)-bornyloxycarbonyl-2-ethynylcarbazole ( 4) were synthesized and polymerized with a Rh catalyst to give the corresponding polymers [poly( 1)–poly( 4)] with moderate M n value of (11.5–92.2) × 10 3 in good yields (77–89%). CD spectroscopic studies revealed that poly( 1), poly( 2) and poly( 4) took predominantly one-handed helical structure in CHCl 3, THF, toluene, and CH 2Cl 2, while poly( 3) did not. Addition of methanol to CHCl 3 solutions of poly( 1) and poly( 2) resulted in the formation of aggregates showing smaller CD signals at 275 and 320 nm. The helical structure of poly( 1) and poly( 2) was very stable against heating. The polymers emitted fluorescence in 0.40–2.90% quantum yields. Poly( 4) exhibited an obvious oxidation peak at 1.10 V. The polymers were thermally stable below 300 °C.