Copolymers of 2-(9H-Carbazol-9-yl)ethyl 2-Methylacrylate and 4-[5-(4-tert-Butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl 2-Methylacrylate: Correlating Hole Drift Mobility and Electronic Structure Calculations with Electroluminescence

Methacrylate monomers functionalized with pendant carbazole and oxadiazole moieties were copolymerized into random copolymers with varying carbazole/oxadiazole ratios. Specifically, the monomers of 2-(9H-carbazol-9-yl)ethyl 2-methylacrylate (CE) and 4-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl 2-methylacrylate (tBPOP) were copolymerized in various ratios, and the inherent hole drift mobilities were assessed through time-of-flight techniques. At a field strength of 345 kV/cm, the homopolymer PCE exhibited a hole mobility of 5.9 x 10(-7) cm(2)/V.s, which was approximately twice the value of the technologically important poly(9-vinylcarbazole), which exhibited a value of 2.8 x 10(-7) cm(2)/V.s. The range of hole mobilities in the copolymers varied from 2.4 x 10(-8) cm(2)/V.s for copolymers containing 50 mol % of the carbazole-containing monomer residue to 3.0 x 10(-7) cm(2)/V.s for copolymers that incorporated 88 mol % of the residue. Density functional theory (B3LYP/6-21G*) and optical absorption derived highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies of CE were -5.39 and -1.94 eV, respectively, while the corresponding oxadiazole monomer (tBPOP) had a HOMO energy of -5.99 eV and a LUMO energy of -2.23 eV. The mean luminous efficiency of coumarin 6 doped single-layer devices constructed from the poly(CE-co-tBPOP) copolymers indicated a relatively flat efficiency of ca. 0.25 cd/A over a wide carbazole mole fraction content of 0.30-0.70.