New poly(4,4′-dicyano-4″-vinyl-triphenylamine) host material for single-layer Ir complex phosphorescent light-emitting devices

Abstract

We report a new host material for iridium complex light-emitting devices, poly(4,4¢-dicyano-4 00 -vinyl-triphenylamine) (PCNVTPA), which was synthesized by nitroxide-mediated free radical polymerization. The incorporation of electron-withdrawing cyano groups led to a significant variation in electronic energy levels and luminescence characteristics in comparison with the parent poly(4-vinyltriphenylamine) (PVTPA). The prepared organosoluble PCNVTPA and PVTPA had number-average molecular weights (M n ) of 10 200 and 23 400, respectively. PCNVTPA exhibited higher thermal stability (T g ¼211 1C) and photoluminescence (PL) quantum efficiency (PLQY) (20%) compared with PVTPA (T g ¼140 1C, PLQY¼3%) because of enhanced rigidity from the cyanosubstituted group. Cyano substitution also led to lower energy levels (HOMO, LUMO, unit: eV) in PCNVTPA (À5.63, À2.52) than in PVTPA (À5.35, À1.89). The emission peak of the Ir complexes was observed in the PL spectra of PVTPA or PCNVTPA/Ir complex blend through efficient energy transfer from the host polymer to the guest Ir complex. Single-layer phosphorescent electroluminescent devices of indium-tin oxide/PEDOT:PSS/PCNVTPA:Ir complexes/Ca:Al showed maximum luminance (2899 cd m À2 ) and luminance efficiency (8.84 cd A À1 ), respectively, which were much higher than those of PVTPA. Such an improvement was probably due to the more efficient hole trapping in Ir complexes by the lower HOMO level or better electron injection from the lower LUMO level of PCNVTPA. The results suggested that the new PCNVTPA could be a good host polymer for the electrophosphorescent device.

Nonconjugated Redox-Active Polymer Mediators for Rapid Electrocatalytic Charging of Lithium Metal Oxides

“…2,2′-Azobis­(isobutyronitrile), 3-chloropropionyl chloride, aluminum­(III) chloride, bis­(2-bromoethyl) ether, glycidol, phenothiazine, phenoxathiine, TEMPO, 4-hydroxy-TEMPO, thianthrene, and tris­(4-bromophenyl)­amine were purchased from Tokyo Chemical Industry Co. Diethylzinc, sodium hydride, and tris­(4-bromophenyl)­ammoniumyl hexachloro­antimonate were obtained from Sigma-Aldrich Co. Other chemicals were purchased from Tokyo Chemical Industry, Sigma-Aldrich, or Kanto Chemical Co. All reagents were used as received unless otherwise noted. 2,2,6,6-Tetramethylpiperidine-1-oxoammonium tetrafluoroborate (TEMPO + BF 4 – ), poly­(TEMPO-substituted glycidyl ether) ( P2a ), poly­(thianthrene-substituted norbornene) ( P4a ), 4-bromo-4′,4″-dicyano­triphenylamine ( 6 ), poly­(4,4′-dicyano-4″-vinyl­triphenylamine) ( P6 ), and poly­(9-vinyl-3,6-dichloro­carbazole) ( P7 ) , were synthesized based on the previous reports. For electrode fabrication, poly­(vinylidene difluoride) (PVdF) (KF Polymer, Kureha Chemical Co.), LiFePO 4 (Toshima Manufacturing Co., 150 mAh/g), LiCoO 2 (Toshima, 140 mAh/g), acetylene black (AB) (Denka Co.), vapor grown carbon fiber (VGCF) (Showa Denko Co.), and single-walled carbon nanotube (SWNT) (Meijo Nano Carbon Co.) were obtained from different companies.…”