• metallopolymers;
  • metal-polymer complexes;
  • oxygen sensors;
  • polyacrylates;
  • radical polymerization


Thumbnail image of graphical abstract

One of the Re complex-containing copolymers synthesized here.

The syntheses of methacrylate- and styrene-based monomers containing substituted pyridine ligands are reported. The preparation of the corresponding homopolymers has been performed by free radical polymerization by using 2,2′-azoisobutyronitrile (AIBN) at 60 °C. The high molecular weights, up to 119 000 g · mol−1, and low glass transition (Tg) values (< −43 °C) have been obtained by the copolymerization reaction with butyl acrylate. The free metal homopolymer and copolymer were subsequently metalated by reaction with Re[phen(CO)3(acetone)]+. All polymer materials have been characterized by conventional experimental techniques, such as gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). UV-Vis and fluorescence spectroscopy have been used to investigate the optical and photophysical properties of the polymers in solid-state films and in solution. 1H NMR spectra confirmed the structure of the synthesized polymers and contributed to the estimate of the monomer sequences in the copolymer chains. Time-resolved and emission-quenching experiments in diluted solutions and on the solid films suggest application of the polymeric materials as oxygen sensors. The morphological aspects of some polymers containing a low amount of rhenium metal complexes have been investigated by scanning electron microscopy (SEM).