Synthesis, chemical modification and second order non-linear optical properties of a new calixarene copolymer

The synthesis of p-tert-butylcalix[4]arene containing polymerizable groups at the lower rim is reported. A calixarene monomer with one methacryloyloxy group at the phenolic rim was copolymerized with methyl methacrylate, yielding linear polymers with pendant calixarene groups in the cone conformation. Chemical modification of these macrocycles by ipso-nitration is described. Thin films were obtained from these materials and studied using m-lines spectroscopy, AFM, and NLO. These modified polymer films exhibited high and stable NLO responses.