SynopsisA voltammetric analysis of the electron-transfer process in poly(viny1ferrocene) (PVF) has been carried out; the results indicate that the electrochemical behavior of ferrocene and PVF are quite similar. The field effects in the macromolecular environment do, however, appear to influence the microscopic potential for oxidation of adjacent ferrocene residues in PVF. Analysis of the slopes of plots of limiting current versus the square root of the rotation speed indicate that only "isolated" ferrocene residues in the polymers are oxidized under the conditions of the rotating-disk electrode experiment.Diffusion coefficients were determined experimentally for ferrocene and its macromolecular analogs were quite close to those simply calculated from the Stokes-Einstein relationship. Further, it was demonstrated that the molecular weight, which is inversely proportional to the diffusion coefficient, could be determined by voltammetric techniques.i L = 0.62nFACD2/3v--/6~1/2
The effect on electrochemical behaviour and electronic charge distribution was examined for a series of 12 vinyl aromatic compounds having the following structural variations : (a) number of cyano-groups attached to the vinyl double bond, (b) substitution para to the vinyl group, and (c) separation between para-substituent and the vinyl group. The radical anion formed in the first one-electron reduction step can either accept a second electron or undergo an irreversible dimerization. Oxidation waves were seen only with those compounds having an amino nitrogen atom para to the vinyl group. Trends in half-wave potentials caused by variation in structure are correlated by means of the Hammett-Zuman and molecular orbital approaches. Due to the strong electron-withdrawing power of the cyano-substituted vinyl group, considerable intramolecular donor-acceptor interaction occurs between the ends of the molecules. This is seen in the measured molecular dipole moments and reflected in the nitrile stretching frequencies and proton chemical shifts. Finally, the efficiences for generation of charge carriers in the compounds as measured by xerographic discharge are related to their solution reduction potentials.THE characterization of the series of mono-, di-, and tricyanovinyl aromatic compounds (1)-(XII) receives its impetus from the possibilities for electrophotographic application shown by members of this class of com-pounds1 Recent reports from these laboratories describe changes of orders of magnitude in charge carrierx -CN
Publication costs assisted by Xerox CorporationThe electrochemical characteristics of dinaphtho[2,l:2',3,]furan-8,13-dione (I), dinaphthotl^^'.Slfuran-7,12-dione (II), and benzo[t>)naphtho[2,3-d]furan-6,ll-dione (III) in acetonitrile have been compared to those of naphthoquinone and anthraquinone in the same solvent system. Electron affinities of 1.22, 1.29, and 1.35 eV (relative to a value of 1.5 eV for p-benzoquinone) have been calculated from the respective one-electron reduction potentials. An estimate of the electron affinities for I and II from charge transfer spectral data gives values of 1.58 and 1.46, respectively.
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