Well‐Defined Ruthenium‐Coordinated Block Copolymers of 2‐Vinylpyridine with 2‐(N‐Carbazolyl)ethyl Methacrylate and Their Optical Properties

Abstract

In order to study the energy‐transfer phenomenon in ruthenium‐coordinated polymers, novel block copolymers from carbazolylethyl methacrylate and 2‐vinylpyridine were prepared by living anionic polymerization; the copolymers possessed varying repeating units and had the desired molecular weight and a narrow‐molecular‐weight distribution. The ruthenium‐coordinated block copolymers were formed by reacting [RuII(tpy)(dmbpy)Cl] with the polymers, in which the pyridine units acted as ligands. Photoluminescence and optical absorption measurements of the coordinated block copolymers were carried out to observe the energy transfer in the complexes. The energy transfer from the carbazole blocks to the ruthenium‐coordinated blocks might take place either by an intra‐ and/or an intermolecular energy‐transfer mechanism. From the optical absorption, photoluminescence, and electroluminescence studies, it was observed that the ease of the energy transfer increased with an increasing number of metal‐complex units. Normalized electroluminescence spectra of the device (ITO/PEDOT/RuIIL2bpolym/TAZ/Alq3/Ag).magnified imageNormalized electroluminescence spectra of the device (ITO/PEDOT/RuIIL2bpolym/TAZ/Alq3/Ag).

Precise Synthesis of Functional Block Copolymers by Living Anionic Polymerization of Vinyl Monomers Bearing Nitrogen Atoms in the Side Chain

“…Pyridine has been extensively employed in the synthesis of metalated complexes of ruthenium and iridium. The coordination of ruthenium and iridium to P2VP or P2VPPy in block copolymers was reported . Photoexcitation of the materials lead to electron and energy transfer from the host functionalities, such as the carbazole and triphenylamine moieties, to transition metal ions (iridium, ruthenium, and platinum) in the complex, resulting in fluorescence and phosphorescence.…”

Structural and Electrical Characterization of a Block Copolymer‐Based Unipolar Nonvolatile Memory Device

“…Moreover, the inserted phenyl group in VPCz extends the conjugation length with respect to the structure of NVC to increase the conductivity. The successful living anionic polymerization of 2VP as a very weak electron acceptor36–38 using an additive of 1,1‐diphenylethylene (DPE)39 was performed without the branching and crosslinking caused by the nucleophilic attack of another carbanion on the pyridine 40, 41. Based on these optimum conditions for the anionic polymerization of VPCz and 2VP, the block copolymerization of VPCz and 2VP was carried out sequentially using DPE after the synthesis of living PVPCz.…”