Synthesis and photophysical study of some new highly thermostable blue fluorescent poly(1,3,4-oxadiazole-imide)s containing dimethylamine groups

Abstract

New poly(1,3,4-oxadiazole-imide)s were synthesized from a diamine containing 1,3,4-oxadiazole ring, 4,4′-diamino-4″-[(2-(4-phenoxy)-5-(4-dimethylaminophenyl)-1,3,4-oxadiazole]triphenylmethane, and different aromatic dianhydrides: 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 9,9-bis[(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) and perylene-3,4,9,10-tetracarboxylic dianhydride. The polymers were easily soluble in polar organic solvents and exhibited high thermal stability, having 5% weight loss in the range of 445-470 °C and glass transition temperature in the domain of 201-244 °C. The optical properties were investigated in different media. The absorption characteristics (intensity, absorption maximum and shape) of investigated compounds depended on their chemical structures and the nature of environment. The emission of these samples was represented by one broadened and blue emission band. The largest and solvent dependent Stokes shifts values were obtained. The fluorescence quantum yield (QY) values of polymer with hexafluoroisopropylidene groups, in tetrahydrofuran solution, depended on the wavelength used for excitation. This is an exception from Kasha's rule and Vavilov's law, which was attributed either to photodecomposition or to the enhancement of intramolecular energy transfer process competing with internal conversion between singlet states. High QY values were obtained for polymers with isopropylidene or fluorene units in dimethyl sulfoxide (polar solvent), which may be due to the strong overlap of electronic transitions of species from system.