Premium
Electrochemical and theoretical study of a family of fully conjugated dendritic oligomers
Author(s) -
Osorio Gabriela,
Frontana Carlos,
Guadarrama Patricia,
FrontanaUribe Bernardo A.
Publication year - 2004
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.751
Subject(s) - chemistry , solvation , electrochemistry , redox , conjugated system , cyclic voltammetry , oligomer , radical ion , computational chemistry , photochemistry , polymer chemistry , molecule , organic chemistry , electrode , ion , polymer
Novel dendritic oligomers of β,β‐dibromo‐4‐ethynylstyrene and formyl‐4‐ethynylstyrene were electrochemically and theoretically studied in order to gain a better insight into their redox behavior. Correlations between calculated ionization and experimental oxidation potentials (anodic peak potentials) were established. The best correlation was obtained when two important effects are considered in the theoretical calculations, probing their strong influence: (a) structural re‐accommodation in the formed radical cation and (b) solvation effects. The effect of dendritic terminal groups (dibromovinyl and formyl groups) was also analyzed. A different redox behavior was observed for these two terminal groups, presumably due to a difference in their oxidation mechanisms. A global chemical transformation for the oxidation of dibromovinyl‐terminated oligomers was proposed, providing a satisfactory explanation of the electrochemical behavior within this family of compounds (presence of adsorptive phenomena). Taking these results into account, it is possible to explain how the cation‐radical species formed in these conjugated dendritic oligomers behave when cyclic voltammetry technique is applied. Copyright © 2004 John Wiley & Sons, Ltd.