Characterization and polymerization of metal complexes of poly(ethylene glycol) diacrylates and the synthesis of polymeric pseudocrown ethers

Polymeric pseudocrown ether networks were formed in situ by the photopolyme rization of poly(ethythene glycol) diacrylate (PEGDA)/transition metal comp lexes. The metal-monomer complex led to a near circular conformation of the monomer in which the two reactive end groups are brought into close proxim ity; thus, the probability of intramolecular cyclization (i.e., pseudocrown ether formation) is increased. Complexes of cobalt(II), nickel(II), zinc(I I), cadmium(II), chromium(III), copper(II), neodymium(III), and lithium wer e characterized using FTIR and UV-vis spectroscopy, Metal-monomer interacti ons were characterized and the importance of coordinated water and anions w as elucidated. A novel technique of replacing coordinated waters by monomer ic ether oxygens was discovered. Pseudocrown ether network formation was co nfirmed via a study of the polymerization kinetics of cobalt(II): PEGDA sys tems in which a decrease in autoacceleration was observed with increasing p seudocrown ether formation.