New preparative procedure for photoluminescent metallopolymers having a biphenyl‐2,2′‐diyl iridium(III) unit bound to a phosphine copolymer ligand

Abstract

We first prepared polymer-bound photoluminescent iridium complexes bearing a cyclometalated 2,2 0 -biphenylene ligand via an easy procedure in which the metallopolymer was synthesized by the reaction of a metal precursor with a polymer ligand. The iridium compound, [Ir(cod)(biph)Cl] 2 (where cod and biph are 1,5-cyclooctadiene and biphenyl-2,2 0 -diyl, respectively), was used as the iridium material, and a copolymer built by the radical copolymerization of 4-styryldiphenylphosphine and methyl methacrylate was employed as the polymer ligand. The obtained metallopolymers were highly crosslinked by iridium atoms forming PÀ ÀIrÀ ÀP bonds. The content of the iridium was experimentally clarified to be in the range of 0.06-0.6 mmol/g of the polymer. Photoluminescence of the iridium polymer in the solid state was observed at 597 nm when the polymer was irradiated at 350 nm. As the Ir content in the copolymer increased to 0.2 mmol/g, the intensity of the luminescence also increased, but more iridium content decreased the intensity. Furthermore, the intensity of the photoluminescence in these photoluminescent polymers depended on the molecular weight of the copolymer ligands. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: [4204][4205][4206][4207][4208][4209][4210][4211][4212][4213] 2006

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

“…31). Solid state luminescence was observed at 597 nm, the intensity of which was dependent on the molecular weight of the copolymer ligands and on the polymer Ir content [48].…”

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

“…While the formation of tris-cyclometallated [118][119][120] and bis-terpyridine iridium(III) complexes [122] are usually rather demanding with respect to temperature and conversion, other types of complexes, e.g., charged bis-cyclometallated complexes bearing bipyridine, can often be obtained in high yields at rather mild conditions. [89,90] Steric demands (e.g., in the case of coordination sites in a conjugated backbone, [119,120] polymer blocks, [121] or crosslinked systems [125] ) is an aspect, which might need to be considered as well. Complex-free polymers are usually easier to investigate by techniques such as SEC, and influences of incorporated complexes are easily revealed by comparing final and precursor polymers.…”

“…[124,125] For the ''decoration'' (I) and the complexation at (co)polymers (II) a high conversion at mild conditions is preferable, enabling the use of stoichiometric amounts by avoiding damage and degradation at the polymer. The ''clicking'' of azides [59] and the coordination to phosphine [124] are two promising examples in this respect.…”

“…[87][88][89][90][118][119][120][121][122][123][124][125] One of the earliest examples of an iridium(III)-complex-containing polymer was obtained by Kim and coworkers in a one-pot, two-step complexation reaction; after treating Ir(acac) 3 with 2-phenylpyridine, the ligand-equipped polymer [poly((2-(4-vinylphenyl)pyridine)co-vinylcarbazole)] was added to achieve the formation of polymer-bound tris-cyclometallated Ir III complexes under rather harsh conditions (170 8C for 12 h). [118] Photoluminescence (PL) investigations in solutions pointed to an intermolecular energy transfer between host and guest rather than an intramolecular one.…”

High Solid State Photoluminescence Quantum Yields and Effective Color Tuning in Polyvinylpyridine Based Zinc(II) Metallopolymers

“…As a consequence, these kind of materials have become attractive and their use in polymeric lightemitting diodes (PLED) supplanted in some cases luminescent doped polymers. [ 20,21 ] We used commercially available poly(4-vinylpyridine) (PVPy) [22][23][24] to coordinate metalloligand moieties onto the pyridine nitrogen. By using this polymer we have matched the benefi ts of the grafted metallopolymers with an easy synthetic route reproducing the same coordination core of the molecular complexes.…”