An ESR study of polymer-Cu(II) complexes in poly(vinyl alcohol), polyacrylamide,and poly(vinyl pyrrolidone) films

Optical and ESR spectra of polymer-Cu(II) complexes in polymer films have been studied. The dependence on F₁ = Cu²⁺]/MU] and F₂ = OH^?]/Cu²⁺], where MU] is the molar concentration of monomeric units of the polymer, has been obtained. Optical spectra and potentiometric titration curves in solution have also been studied. There exists a buffer region 0 ? F₂ ? 2. Optical spectra in films are slightly different from those in solutions. At least five different ESR signals, designated as A, B, C or D, and E, have been found in poly(vinyl alcohol)-Cu(II). These signals appear successively with increasing F₂. Assignments are proposed as follows. Signal A (F₂ ≈ 0), also found in poly(acrylamide)-Cu(II) and poly(vinyl pyrrolidone)-Cu(II), is due to a single Cu(II) coordinated with two water molecules and chelated with two oxygens or nitrogens attached to the polymer. A chain of Cu(II) ions singly and double bridged with OH^? ions is responsible for the B signal (F₂ ≈ 1). The C and D signals (F₂ ≈ 2) appear to be caused, respectively, by a dimeric Cu(II) complex singly or doubly bridged with OH^? ions. The E signal (F₂ ≈ 7) appears to be due to a monomeric Cu(II) complex, different from that responsible for the A signal.