ABSTRACT
The electronic structures of eight bathophenanthroline derivatives were elucidated by DFT calculations, and four representatives of which CZBP, m-CZBP, m-TPAP, and BPABP were synthesized and employed as the hosts to afford highly efficient phosphorescent OLEDs. The calculated molecular orbital energies agree well with the experimental results, which further demonstrates that the localization of HOMO and LUMO at the respective hole- and electron-transporting moieties is desirable in bipolar molecular designs.
ABSTRACT
The polymer poly(4{2-[N,N-bis(trimethylsilyl)amino]ethyl}styrene), prepared by anionic polymerization and of low polydispersity (M(w)/M(n) = 1.10-1.18), has been derivatized by amide linkage to [Ru(II)(bpy)(2)(4-(CO-)-4'-CH(3)-bpy)-](2+) (bpy is 2,2'-bipyridine; 4-(CO-)-4'-CH(3)-bpy is 4-carbonyl-4'-methyl-2,2'-bipyridine). Unreacted amine sites were converted into acetamides by treatment with acetic anhydride to give derivatized polymers of general formula [PS-CH(2)CH(2)NHCO(Ru(II)(n)()Me(m)())](PF(6))(2)(n)(), where m + n = 11, 18, or 25, PS represents the polystyrene backbone, and Ru(II) and Me represent the attached complex and acetamide, respectively. Spectral and electrochemical properties of the derivatized polymers are similar to those of the model [Ru(bpy)(2)(4-CONHCH(2)CH(2)C(6)H(5)-4'-CH(3)-bpy)](2+) (4-CONHCH(2)CH(2)C(6)H(5)-4'-CH(3)-bpy is 4'-methyl-2,2'-bipyridinyl-4-(2-phenylethylamide)), but emission quantum yields (phi(em)) and time-resolved emission decays are slightly dependent on the level of Ru(II) loading, with nonexponential, irradiation-dependent decays appearing at high loadings. The decays could be fitted satisfactorily to the first derivative of the Williams-Watts distribution function. These results are discussed with reference to possible structural and multichromophoric effects on excited-state decay.
ABSTRACT
The polymer poly[4-(2-aminoethyl)styrene], prepared by living anionic polymerization, has been derivatized by amide coupling to [Ru(II)(vbpy)(2)(4-CO(2)H-4'-CH(3)bpy)](2+) (vbpy is 4-vinyl-4'-methyl-2,2'-bipyridine; 4-CO(2)H-4'-CH(3)bpy is 4-methyl-2,2'-bipyridine-4'-carboxylic acid). The resulting "macromer" can be electropolymerized on a variety of electrode materials by reductive electropolymerization. Compared to similar films of poly[Ru(II)(vbpy)(3)](PF(6))(2): (1) the macromeric films are considerably rougher, apparently having open, local microporous structures; (2) they undergo comparable rates of intrafilm charge transfer; and (3) they have shortened metal-to-ligand charge transfer (MLCT) excited state lifetimes, apparently due to quenching by film-based trap sites. Stable films of a mixed polymer have also been prepared by sequential addition of [Ru(II)(bpy)(2)(4-CO(2)H-4'-CH(3)bpy)](2+) and then the vbpy derivative.
