Study of Supramolecular Side-Chain Copolymers Containing Light-Emitting H-Acceptors and Electron-Transporting Dendritic H-Donors

Abstract

A novel light-emitting hydrogen-bonded (H-) acceptor PBB (M1) containing three conjugated aromatic rings, including one pyridyl terminus and two lateral methoxyl groups (on the middle ring), was successfully synthesized via Horner−Wadsworth−Emmons (HWE) olefination and Sonogashira coupling reaction. Moreover, different molar ratios of light-emitting H-acceptor monomer PBB (M1) and hole-transporting monomer CAZ (M2) bearing a carbazole unit were copolymerized through free radical polymerization to obtain light-emitting and hole-transporting H-acceptor copolymers (P1−P5). H-acceptor copolymers P3 and P4 were complexed with different generations of dendritic H-donors (G1COOH−G3COOH) bearing 1,3,4-oxadiazole (OXD) dendrons and terminal benzoic acids via H-bonded self-assembly to form supramolecular side-chain copolymers (i.e., H-bonded dendritic complexes). In contrast to H-acceptor homopolymer P1 (HPBB), H-acceptor copolymers P2−P4 incorporated with carbazole (CAZ) moieties effectively enhance the glass transition temperatures (Tgs) and minimize the interchain interations of the light-emitting H-acceptor units, and similar effects occur in their H-bonded dendritic complexes. In addition, red shifts of photoluminescence (PL) emissions in H-bonded dendritic complexes can be tuned up to 61 nm. Furthermore, H-bonded dendritic complexes excited at 305 nm of OXD absorption can create a stronger fluorescence than that excited at 397 nm of PBB absorption, indicating that the intensity of the sensitized emission of PBB (by energy transfer from OXD absorption at 305 nm) is even stronger than that of a direct emission of PBB (by merely PBB absorption at 397 nm). The OXD dendritic wedges in H-bonded dendritic complexes can lower the LUMO energy levels and provide a better electron injection property. H-acceptor polymer P4 and its H-bonded dendritic complexes showed electroluminescence (EL) emissions in the range of 464−519 nm from blue to green. In addition, a PLED device containing H-bonded dendritic complex P4/G1COOH showed an EL emission of 519 nm under a turn-on voltage of 6.5 V, with a maximum luminance of 408 cd/m2 at 18 V and a luminance efficiency of 0.39 cd/A at 100 mA/cm2, respectively.