TY - JOUR
T1 - Electrochemical and spectroscopic investigation of the influence of acid-base chemistry on the redox properties of 2,5-dimercapto-1,3,4-thiadiazole
AU - Shouji, Eiichi
AU - Yokoyama, Yasuyuki
AU - Pope, John M.
AU - Oyama, Noboru
AU - Buttry, Daniel A.
PY - 1997/4/10
Y1 - 1997/4/10
N2 - The UV-vis spectroscopy and cyclic voltammetry of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) were studied in the absence and presence of pyridine (Py) or triethylamine (TEA) in acetonitrile solutions in order to examine the influence of acid-base processes on the redox behavior of DMcT. In solutions containing Py, DMcT can be singly deprotonated to give the anionic species, DMcT-. In solutions containing TEA, DMcT can be either singly or doubly deprotonated to give the anionic species, DMcT-, or the dianion, DMcT2-, depending on the stoichiometry. These acid-base processes were monitored using UV-vis spectroscopy, and those results are reported here. The cyclic voltammetry of both systems was also examined in the absence and presence of Py or TEA. These experiments clearly showed that deprotonation of DMcT results in facilitation of its electrochemical oxidation, leading either to a disulfide-containing dimer or a disulfide-containing polymer, depending on conditions. The relevance of these results to the use of DMcT as a cathode material in lithium secondary batteries is discussed.
AB - The UV-vis spectroscopy and cyclic voltammetry of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) were studied in the absence and presence of pyridine (Py) or triethylamine (TEA) in acetonitrile solutions in order to examine the influence of acid-base processes on the redox behavior of DMcT. In solutions containing Py, DMcT can be singly deprotonated to give the anionic species, DMcT-. In solutions containing TEA, DMcT can be either singly or doubly deprotonated to give the anionic species, DMcT-, or the dianion, DMcT2-, depending on the stoichiometry. These acid-base processes were monitored using UV-vis spectroscopy, and those results are reported here. The cyclic voltammetry of both systems was also examined in the absence and presence of Py or TEA. These experiments clearly showed that deprotonation of DMcT results in facilitation of its electrochemical oxidation, leading either to a disulfide-containing dimer or a disulfide-containing polymer, depending on conditions. The relevance of these results to the use of DMcT as a cathode material in lithium secondary batteries is discussed.
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U2 - 10.1021/jp962704u
DO - 10.1021/jp962704u
M3 - Article
AN - SCOPUS:0000892005
SN - 1520-6106
VL - 101
SP - 2861
EP - 2866
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 15
ER -