| The molecular imprinting technique has been demonstrated for organic molecule immobilized within highly crosslinked porous network polymers. In effect, the resulting polymer retains a memory of the conformation of the organic template present during polymerization. The present work demonstrates the extension of this template effect to metallo-network polymers. Metallo-network polymers are formed by utilizing inorganic complexes as comonomers in the formation of highly crosslinked porous network polymers. In nearly all systems to date the template in metallo-network polymers remains primarily organic in nature, as a ligand bound to the metal. The metal center in such systems serves as a binding site for the template molecule. This is demonstrated by the reversible binding of CO to immobilized copper(I) complexes as monitored by diffuse reflectance FT-IR spectroscopy. In addition, the present work offers the first example of the template effect, in highly crosslinked network polymers, that is directed by the transition metal. Six-coordinate cobalt(III) Schiff base complexes were immobilized within a highly crosslinked polymer of ethylene glycol dimethacrylate. The orientation of the salicylaldehyde groups, in the form of either tetradentate or pentadentate Schiff base ligands, is directed by the cobalt(III) centers. The resulting polymer is rigid enough to maintain the orientation of the salicylaldehyde groups that result from the removal of the cobalt(III) centers. The tetradentate or pentadentate ligand sites can be reformed by adding the appropriate diamine to the polymer with... |
