Alexander M. Breul

Light-harvesting of polymerizable 4-hydroxy-1,3-thiazole monomers by energy transfer toward photoactive Os(II) metal complexes in linear polymers

A polymer library consisting of a series of three fluorescing monomers (i.e., blue, yellow and red-emitting) based on 4-hydroxy-1,3-thiazole chromophores as well as an Os(II) metal complex containing monomer was synthesized. These materials were characterized using 1H NMR spectroscopy, size-exclusion chromatography (SEC) as well as TGA and DSC measurements. The optical properties were investigated utilizing UV-vis absorption and emission measurements. The tailor-made optical properties of the monomer units facilitate energy transfer from the blue over the yellow and red chromophores to the photoactive Os(II) polypyridyl moiety. For this purpose, the energy transfer was monitored using excitation–emission correlation spectroscopy.

Incorporation of Polymerizable Osmium(II) Bis-terpyridine Complexes into PMMA Backbones

For the first time, an Os(II) bis-terpyridine complex bearing a polymerizable methacryloyl function was synthesized and subsequently copolymerized with MMA using the RAFT polymerization technique. The well-defined polymer was analyzed by SEC, ESI-TOF MS, 1H NMR spectroscopy as well as UV–Vis absorption and emission spectroscopy. The lifetime as well as redox potentials of the complex and the corresponding polymer were also determined. Additionally, the film forming properties of the polymer were investigated and preliminary UV–Vis absorption as well as emission experiments were carried out with a second donor pendant polymer revealing energy transfer from the donor to the Os(II) complex.Graphical AbstractThe synthesis and subsequent polymerization of a methacrylate functionalized Os(II) bis-terpyridine complex is described. The copolymerization with MMA resulted in a polymer that features the well-defined optical and electrochemical properties of the complex combined with typical polymer properties.

Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex.