aPolymers that exhibit changes of their luminescence colour in response to external stimuli are attractive candidates for sensing systems. We herein report the preparation of europium-based metallosupramolecular polymers, which can be processed into films and coatings that display readily detectable luminescence colour changes in response to various types of analytes. 14 These low-molecular weight solvent-based sensory systems demonstrate the potential benefits of luminescence colour changes, and similar responses were also achieved with metallosupramolecular polymer (MSP) networks that feature combinations of transition or lanthanide metal ions due to a selective quenching of some of the metal-based emission. 15,16 A direct monitoring of the disassembly with a potential increase in sensitivity may be achieved by employing ligands that feature a distinct emission in the visible range, which has, to the best of our knowledge, not been explored in polymeric solid-state materials so far. We herein report a lanthanide-based MSP system that features a distinct and clearly visible emission colour change due to the vastly different emission characteristics of the metalligand complex, and the telechelic, ligand-carrying macromonomer. Red-light emitting MSP films are obtained upon assembling the macromonomer with europium perchlorate and a clearly visible luminescence colour change is observed in response to different stimuli such as heat, exposure to solvents, or other analytes that disrupt or alter the metal-ligand complexes. The distinct colour change constitutes a visually detectable signal that indicates exposure to the various analytes and may allow for an in situ optical monitoring.
MetalThe basis of the approach used in our study are tridentate Mebip ligands, which are known to act as efficient "antennas" for lanthanide ions.17 However, Mebip itself does not fluoresce in the visible range. To shift the fluorescence of this motif into the visible range, an extension of the conjugated π-system was pursued. Thus, 2,6-bis(1′-methylbenzimidazolyl)-4-bromopyridine was prepared following literature procedures and its coupling to 4-ethynylaniline under Sonogashira conditions yielded the desired π-extended Mebip derivative (Fig. S1 †). 18,19 Subsequently, this ligand was coupled to dodecanoic acid and bis-carboxylic acid functionalised telechelic poly(ethylene-co- † Electronic supplementary information (ESI) available: A comprehensive account of all experimental details, including synthetic procedures, analytical data, and NMR spectra of all novel compounds is provided. See