Synthesis, Photoluminescence, and Electrochromism of Novel Aromatic Poly(amine-1,3,4-oxadiazole)s Bearing Anthrylamine Chromophores

Two novel poly(amine-hydrazide)s were prepared from the polycondensation reactions of the dicarboxylic acid, 9-[N,N-di(4-carboxyphenyl)amino]anthracene (1), with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH) via the Yamazaki phosphorylation reaction, respectively. The poly(amine-hydrazide)s were readily soluble in many common organic solvents and could be solution cast into transparent films. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass-transition temperatures (T-g) in the range of 182-230 degrees C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300-400 degrees C. The resulting poly(amine-1,3,4-oxadiazole)s had useful levels of thermal stability associated with high T-g (263-318 degrees C), 10% weight-loss temperatures in excess of 500 degrees C, and char yield at 800 degrees C in nitrogen higher than 55%. These organo-soluble anthrylamine-based poly(amine-hydrazide)s and poly (amine-1,3,4-oxadiazole)s exhibited maximum UV-vis absorption at 346-349 and 379-388 nm in N-methyl-2-pyrrolidone (NMP) solution, respectively. Their photoluminescence spectra in NMP solution showed maximum bands around 490-497 nm in the green region. The poly(amine-hydrazide) I-IPH showed a green photoluminescence at 490 nm with PL quantum yield of 29.9% and 17.0% in NMP solution and film state, respectively. The anthrylamine-based poly(amine-1,3,4-oxadiazole)s revealed a electro-chromic characteristics with changing color from the pale yellow neutral form to the red reduced form when scanning potentials negatively from 0.00 to -2.20 V. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1584-1594, 2009