Spectrophotometric and thermal studies of the reaction of iodine with nickel(II) acetylacetonate

The reaction of iodine (acceptor) and nickel(II) acetylacetonate (donor) was studied photometrically in different solvents such as chloroform, dichloromethane and carbon tetrachloride at room temperature. The results indicate the formation of a 1:1 charge-transfer complex in each solvent and the iodine complex is formulated as the triiodide species {[}Ni(acac)(2)](2)I+.I-3(-), based on the characteristic electronic absorptions of the I-3(-) ion at 361 and 285 nm, as well as on the far infrared absorption bands characteristic of the I-3(-) ion with C-2v symmetry. These bands are observed at 132, 101 and 84 cm(-1) and are assigned to nu(a)(I-I), nu(s)(I-I) and delta(I-3(-)), respectively. The values of the equilibrium constant (K), absorptivity (epsilon) and oscillator strength (f) of the iodine complex are shown to be strongly dependent on the type of solvent used. The important role played by the solvent is suggested to be mainly due to the interaction of the ionic complex with the solvent. The proposed structure of the new solid triiodide charge-transfer complex reported in this study is further supported by thermal and mid-infrared measurements.