Electrochemical and spectroscopic investigation of the influence of acid-base chemistry on the redox properties of 2,5-dimercapto-1,3,4-thiadiazole

Eiichi Shouji, Yasuyuki Yokoyama, John M. Pope, Noboru Oyama, Daniel Buttry

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)2861-2866
Number of pages6
JournalJournal of Physical Chemistry B
Volume101
Issue number15
StatePublished - Apr 10 1997
Externally publishedYes

Fingerprint

Pyridine
pyridines
disulfides
chemistry
Ultraviolet spectroscopy
acids
Cyclic voltammetry
Acids
storage batteries
Deprotonation
Secondary batteries
electrochemical oxidation
lithium batteries
Electrochemical oxidation
Acetonitrile
Stoichiometry
Dimers
spectroscopy
acetonitrile
stoichiometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Electrochemical and spectroscopic investigation of the influence of acid-base chemistry on the redox properties of 2,5-dimercapto-1,3,4-thiadiazole. / Shouji, Eiichi; Yokoyama, Yasuyuki; Pope, John M.; Oyama, Noboru; Buttry, Daniel.

In: Journal of Physical Chemistry B, Vol. 101, No. 15, 10.04.1997, p. 2861-2866.

Research output: Contribution to journalArticle

@article{00aad493e439416d98d7457c7c30cc00,
title = "Electrochemical and spectroscopic investigation of the influence of acid-base chemistry on the redox properties of 2,5-dimercapto-1,3,4-thiadiazole",
abstract = "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.",
author = "Eiichi Shouji and Yasuyuki Yokoyama and Pope, {John M.} and Noboru Oyama and Daniel Buttry",
year = "1997",
month = "4",
day = "10",
language = "English (US)",
volume = "101",
pages = "2861--2866",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "15",

}

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

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.

UR - http://www.scopus.com/inward/record.url?scp=0000892005&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000892005&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000892005

VL - 101

SP - 2861

EP - 2866

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 15

ER -