End-functionalization of a vinylidene fluoride oligomer in coordination nanochannels

Abstract

The utility of basic sites of porous coordination polymers (PCPs) for the end-functionalization of oligo(vinylidene fluoride) (OVDF) is demonstrated. Densely arranged carboxylate moieties on the PCP pore walls act as basic sites and allow the efficient elimination reaction of the terminal group of OVDF to proceed. The progress of the reaction of an OVDF precursor in the PCP nanochannels was evidenced using solid state ¹⁹F NMR spectroscopy. From ¹⁹F and ¹H NMR and IR measurements of the product isolated from the composite obtained, the terminal –CH₂CF₂I moiety of OVDF was shown to be successfully converted to a –CHCF₂group. Because of the large surface area of the PCP materials, the OVDF precursor easily accessed the basic sites, resulting in a large increase in the rate of the elimination reaction. In addition, a notable effect of the porous structure of PCPs upon the elimination reaction was observed.