A. Benito et al., PREDICTING THE MAXIMUM OXIDATION POTENTIAL SHIFT IN REDOX-ACTIVE PH-RESPONSIVE MOLECULES IN THEIR ELECTROSTATIC INTERACTION WITH SUBSTRATES, Journal of the Chemical Society. Faraday transactions, 93(12), 1997, pp. 2175-2180
Citations number
32
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
Potentiometric and electrochemical studies have been carried out in TH
F-H2O (60:40 v/v) and H2O on several ferrocene-containing pH-responsiv
e molecules and the acidity constants of the reduced species (K-m), th
e 'oxidised' species (K-m(n)) and the maximum oxidation potential shif
t due to the binding process of L with protons (Delta E) have been det
ermined. From these values, and Delta E data in MeCN, MeCN-H2O (80:20
v/v), THF-H2O (80:20 v/v) and H2O, an empirical equation based on a Co
ulomb charge model, is obtained which accounts for the maximum oxidati
on potential shift as a function of the charge of the oxidised electro
active framework, the charge of the substrate, the number of electrons
involved in the electrochemical process, the number of redox-active u
nits, the distance between the redox-active groups and the substrate a
nd the macroscopic relative permittivity of the medium.