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ELECTROINITIATED POLYMERIZATION OF HALOPHENOLS - ELECTROINITIATION POTENTIAL LUMO RELATIONS

1988-11-01
TURKER, L
KISAKUREK, D
SEN, S
Toppare, Levent Kamil
Akbulut, Ural
Electroinitiated polymerizations can be carried out by direct electron transfer via constant potential electrolysis.1–3 In doing so, the anodic (Ep, a) and the cathodic (Ep, c) potentials of the monomers must be measured by cyclic voltammetry. The cathodic peak potentials of halophenols were measured on Pt0 electrode versus Ag0/Ag+ in acetonitrile. Electroinitiated polymerization of bis(pyridine), bis(4‐chloro‐2,6‐dibromophenoxide) copper (II) complex was studied in dimethylformamide‐tetrabutylammonium fluoroborate by direct electron transfer from the cathode. Poly(phenylene oxides) obtained from the anolyte revealed that the monomer undergoes 1,2 as well as 1,4 addition reactions. Lowest unoccupied molecular orbital energies of the monomers were calculated by Hückel molecular orbital theory. The experimental Ep, c values were correlated to theoretical LUMO energies and electron densities using a multivariable linear regression model.