Self‐assembly of H‐bonded side‐chain and cross‐linking copolymers containing diblock‐copolymeric donors and single/double H‐bonded light‐emitting acceptors

A series of diblock‐copolymers were synthesized through anionic polymerization of styrene and tert‐butyl methacrylate (tBuA) with different monomer ratios, and analogous block‐copolymeric derivatives (PS‐b‐PAA)s with monofunctional carboxylic acid groups were obtained by further hydrolyzation as hydrogen‐bonded (H‐bonded) proton donors. Via H‐bonded interaction, these diblock‐coplymeric donors (PS‐b‐PAA)s were incorporated with luminescent mono‐pyridyl/bis‐pyridyl acceptors to form single/double H‐bonded supramolecules, that is, H‐bonded side‐chain/cross‐linking copolymers, respectively. The supramolecular architectures formed by donor polymers and light‐emitting acceptors were influenced by the ratio of acid blocks in the diblock copolymeric donors and the type of single/double H‐bonded light‐emitting acceptors. Their thermal and luminescent properties can be adjusted by H‐bonds, and more than 100 nm of red‐shifted photoluminescence (PL) emissions were observed, which depend on the degrees of the H‐bonding interactions. Self‐assembled phenomena of amphiphilic dibolck copolymers and their H‐bonded complexes were confirmed by TEM micrographs, and supramolecular microphase separation of spherical micelle‐like morphology was demonstrated to affect the photophysical properties. Polymer light‐emitting diode (PLED) devices containing H‐bonded complexes showed electroluminescence (EL) emissions of 503–560 nm under turn‐on voltages of 7.5–9.0 V, maximum power efficiencies of 0.23–0.37 cd/A (at 100 mA/cm²), and maximum luminances of 318–519 cd/m² (around 25 V). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4685–4702, 2009