TY - JOUR
T1 - Electrochemistry of TCNQF2 in acetonitrile in the presence of [Cu(CH3CN)4]+
T2 - Electrocrystallisation and characterisation of CuTCNQF2
AU - Vo, Nguyen T.
AU - Martin, Lisandra L.
AU - Bond, Alan M.
PY - 2018/8/1
Y1 - 2018/8/1
N2 - The bulk electrochemical reduction of TCNQF2 (where TCNQF2 = 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of [Cu(CH3CN)4]+ leads to the electrocrystallisation of TCNQF2 1− and TCNQF2 2− materials, identified and proposed as CuITCNQF2 I− and CuI 2(TCNQF2 II−)(CH3CN)2, respectively. The existence of two forms of each solid was established by cyclic voltammetry. The low solubility of both CuITCNQF2 I− and CuI 2(TCNQF2 II−)(CH3CN)2 solids, facilitated detection of a solid-solid transformation in the presence of [Cu(CH3CN)4]+. CuITCNQF2 I− was synthesized chemically as a dark blue microcrystalline solid by reaction of TCNQF2 and CuI in CH3CN, as well as electrochemically. Electronic and vibrational spectroscopic methods confirmed the CuITCNQF2 I− product obtained by either method was structurally identical. Powder X-ray diffraction studies of CuITCNQF2 I− gave a closely related pattern to that for the thermodynamically stable CuITCNQI− phase II (a coordination polymer) rather than the kinetically favoured CuITCNQI− phase I. Scanning electron microscopy established the dominant morphology, derived from both electrocrystallized and chemically synthesised samples, were the same. The conductivity of CuITCNQF2 I− as a film on FTO glass was 6.0 × 10−6 S cm−1, which lies in the semiconducting range.
AB - The bulk electrochemical reduction of TCNQF2 (where TCNQF2 = 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of [Cu(CH3CN)4]+ leads to the electrocrystallisation of TCNQF2 1− and TCNQF2 2− materials, identified and proposed as CuITCNQF2 I− and CuI 2(TCNQF2 II−)(CH3CN)2, respectively. The existence of two forms of each solid was established by cyclic voltammetry. The low solubility of both CuITCNQF2 I− and CuI 2(TCNQF2 II−)(CH3CN)2 solids, facilitated detection of a solid-solid transformation in the presence of [Cu(CH3CN)4]+. CuITCNQF2 I− was synthesized chemically as a dark blue microcrystalline solid by reaction of TCNQF2 and CuI in CH3CN, as well as electrochemically. Electronic and vibrational spectroscopic methods confirmed the CuITCNQF2 I− product obtained by either method was structurally identical. Powder X-ray diffraction studies of CuITCNQF2 I− gave a closely related pattern to that for the thermodynamically stable CuITCNQI− phase II (a coordination polymer) rather than the kinetically favoured CuITCNQI− phase I. Scanning electron microscopy established the dominant morphology, derived from both electrocrystallized and chemically synthesised samples, were the same. The conductivity of CuITCNQF2 I− as a film on FTO glass was 6.0 × 10−6 S cm−1, which lies in the semiconducting range.
KW - Chemical synthesis of CuTCNQF
KW - Cyclic voltammetry
KW - Electrocrystallisation of CuTCNQF and Cu (TCNQF )(CHCN)
KW - Electronic and vibrational spectroscopy
KW - Morphology
UR - http://www.scopus.com/inward/record.url?scp=85047092451&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2018.04.010
DO - 10.1016/j.ica.2018.04.010
M3 - Article
AN - SCOPUS:85047092451
VL - 480
SP - 91
EP - 100
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
ER -