Macromolecules, Vol.47, No.5, 1594-1603, 2014
Synthesis of Optically Active Conjugated Polymers Bearing m-Terphenylene Moieties by Acetylenic Coupling Polymerization: Chiral Aggregation and Optical Properties of the Product Polymers
The acetylenic coupling polymerization of D-hydroxyphenylglycine-derived m-terphenylene diynes 1-5 using Pd/Cu catalyst gave the corresponding polymers [poly(1)-poly(5)] with M-n = 12 000-60 000 in 53-89% yields. The polymers were soluble in THF and DMF. CD and UV-vis spectroscopic analysis revealed that p,p'-phenyleneethynylene-linked poly(1), poly(3), and poly(5) formed chiral higher-order structures in THF/H2O mixtures, while m,m'-phenyleneethynylene-linked poly(2) and poly(4) did not. The sign of CD signal of poly(1) was reasonably predicted by time-dependent density functional calculations of the model system. The polymers emitted fluorescence with quantum yields ranging from 0.2-14.8%.