Synthesis, Structural Characterization, and Thermal and Optical Properties of Hyperbranched Poly(aminoarylene)s

A group of new hyperbranched poly(aminoarylene)s (hb-PAAs) were prepared by the copolycyclotrimerizations of diynes 1−3 and triyne 4 with monoynes 5 and 6 catalyzed by TaBr5 and CpCo(CO)2−hν. hb-PAAs with high molecular weights (Mw up to 26600) were obtained in high yields (up to 93%). Whereas the hb-PAAs synthesized from diphenylaminodiynes contained no internal cyclic structures, their counterparts from triphenylaminotriyne possessed small- and medium-size macrocyclic structures due to the ortho- and meta-linkages of the newly formed 1,2,4- and 1,3,5-substituted benzene rings. All the hb-PAAs are thermally very stable with degradation temperatures up to ∼580 °C and emit bright blue lights in dilute solutions as well as in thin films.