TY - JOUR
T1 - Chemically Induced Release of Charge from a Rectifying Polymer Based on Viologen and Quinone Subunits
AU - Smith, Diane K.
AU - Tender, Leonard M.
AU - Lane, Gregg A.
AU - Licht, Stuart
AU - Wrighton, Mark S.
PY - 1989/2/1
Y1 - 1989/2/1
N2 - Charge associated with the reduction of quinone, 2e−+ 2H++ Q->QH2, can be trapped at low pH in the electrode-confined siloxane polymer, (BV-Q-BV6+)n, which is derived from a monomer that consists of a benzoquinone unit flanked by two benzyl viologen units. 2ne−s can be released from the polymer by raising the solution pH to neutral or basic pH where the viologen can reoxidize the QH2to Q, ultimately delivering the charge to the electrode. Chemical redox reagents, added to the polymer film, can also be used to release the charge and deliver it to the electrode. The use of I3−/I−and Fe(CN)63-/4-as charge-release mediators is demonstrated. Oxidation of QH2centers occurs when the potential of an electrode modified with (BV-Q-BV6+)nis brought close to E°'(I3−/I−) or E° '( Fe(CN)63-/4-). Because Fe(CN)63-/4-is concentrated by the polycationic (BV-Q-BV6+)npolymer, only very small solution concentrations, approximately 1 μM, are required to effectively mediate the oxidation of QH2.
AB - Charge associated with the reduction of quinone, 2e−+ 2H++ Q->QH2, can be trapped at low pH in the electrode-confined siloxane polymer, (BV-Q-BV6+)n, which is derived from a monomer that consists of a benzoquinone unit flanked by two benzyl viologen units. 2ne−s can be released from the polymer by raising the solution pH to neutral or basic pH where the viologen can reoxidize the QH2to Q, ultimately delivering the charge to the electrode. Chemical redox reagents, added to the polymer film, can also be used to release the charge and deliver it to the electrode. The use of I3−/I−and Fe(CN)63-/4-as charge-release mediators is demonstrated. Oxidation of QH2centers occurs when the potential of an electrode modified with (BV-Q-BV6+)nis brought close to E°'(I3−/I−) or E° '( Fe(CN)63-/4-). Because Fe(CN)63-/4-is concentrated by the polycationic (BV-Q-BV6+)npolymer, only very small solution concentrations, approximately 1 μM, are required to effectively mediate the oxidation of QH2.
UR - https://www.scopus.com/pages/publications/0000467245
U2 - 10.1021/ja00185a047
DO - 10.1021/ja00185a047
M3 - Article
AN - SCOPUS:0000467245
SN - 0002-7863
VL - 111
SP - 1099
EP - 1105
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -