Controlling polymer properties through dynamic metal-ligand interactions: supramolecular cruciforms made easy

A straightforward methodology towards the supramolecular synthesis of novel organometallic polymers with attractive optical properties is presented. By coordinating bifunctional fluorescent cruciform molecules through ditopic metalated pincer complexes (Pd or Pt), we have synthesized a new class of well-defined coordination polymers that have controllable and tunable physical and photophysical properties. The formation of these new materials by employing metal coordination was monitored by (1)H NMR spectroscopy, the association strength of the metal-ligand interaction was measured by isothermal titration calorimetry, the solution polymeric properties were evaluated by viscometry, and the optical properties were measured and observed by fluorescence spectroscopy. The fast and quantitative synthesis of a wide range of prefabricated monomeric cruciform and metalated-pincer-complex components will allow for the rapid generation, growth, and optimization of this new class of functional polymers, which have potential electronic and optical applications.