Synthesis, optical and electrochemical properties of novel hole-blocking poly(biphenylene-1,3,4-oxadiazole) containing electron-withdrawing trifluoromethyl groups

New poly(biphenylene-1,3,4-oxadiazole) P1 and poly(biphenylene hydrazide) P2 containing electron-withdrawing trifluoromethyl group at the 2 and 2′ positions of biphenyl moiety were synthesized. The biphenyl is forced to adapt a non-coplanar conformation due to the bulky trifluoromethyl group. High quality polymer P1 thin film can be easily obtained by thermal cyclodehydration from its soluble polyhydrazide precursor P2. The polymer P1 exhibited good thermal stability with glass transition temperature of 234 °C and 5% decomposition temperature of 469 °C. The optical and electrochemical properties were investigated by UV–vis spectroscopy, photoluminescence spectroscopy and cyclic voltammetry. For polymer P1 film, two absorption peaks at 370 and 414 nm were observed. It also exhibited a photoluminescent peak at 555 nm when excited by 414 nm light. The cyclic voltammetric studies revealed that polymer P1 had extremely low HOMO (−6.85 eV) and LUMO (−3.71 eV) energy levels due to the presence of strong electron-withdrawing trifluoromethyl group. It also exhibited a large energy gap (3.14 eV) which is an indication of short conjugation length resulted from non-coplanar biphenyl structure. Its HOMO energy was even lower than that of widely used hole-blocking material, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole PBD (−6.30 eV). The low LUMO energy of polymer P1 could allow the easier electron injection from air-stable cathode such as aluminum. The good electron transfer ability was also shown by measuring the current density of electron-only devices with the structures of Al/P1 (150 nm)/Alq3 (50 nm)/Al and Al/Alq3 (200 nm)/Al. Combined with high thermal stability and amorphous morphology, polymer P1 would be a promising candidate as the hole-blocking material for organic light-emitting diodes.