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Lisandra L. Martin - One of the best experts on this subject based on the ideXlab platform.
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role of water in the dynamic disproportionation of zn based tcnq f 4 coordination polymers tcnq Tetracyanoquinodimethane
Inorganic Chemistry, 2014Co-Authors: Ayman Nafady, Alan M. Bond, Naomi L Haworth, Lisandra L. MartinAbstract:Intriguingly, coordination polymers containing TCNQ2– and TCNQF42– (TCNQ = 7,7,8,8-Tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane, both designated as TCNQ(F4)2–) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN2– revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN2+. Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– ⇌ TCNQ(F4)MeCN + TCNQ(F4)MeCN2– is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10–10; TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN2+ + 2 TCNQ(F4)MeCN•– ⇌ ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble Z...
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identification of tcnqf4 redox levels using spectroscopic and electrochemical fingerprints tcnqf4 2 3 5 6 tetrafluoro 7 7 8 8 Tetracyanoquinodimethane
Inorganica Chimica Acta, 2013Co-Authors: Alan M. Bond, Lisandra L. MartinAbstract:Abstract Solution and solid state methods for the identification of TCNQF 4 , TCNQF 4 − and TCNQF 4 2 − redox levels (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) are described. Solution phase UV–Vis spectroscopy and electrochemistry can be used for both qualitative and quantitative determinations, while infrared and Raman spectroscopies are very powerful for solid state identification. Analogous strategies can also be applied to other TCNQ derivatives (TCNQ = 7,7,8,8-Tetracyanoquinodimethane).
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Identification of TCNQF4 redox levels using spectroscopic and electrochemical fingerprints (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane)
Inorganica Chimica Acta, 2013Co-Authors: Alan M. Bond, Lisandra L. MartinAbstract:Abstract Solution and solid state methods for the identification of TCNQF 4 , TCNQF 4 − and TCNQF 4 2 − redox levels (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) are described. Solution phase UV–Vis spectroscopy and electrochemistry can be used for both qualitative and quantitative determinations, while infrared and Raman spectroscopies are very powerful for solid state identification. Analogous strategies can also be applied to other TCNQ derivatives (TCNQ = 7,7,8,8-Tetracyanoquinodimethane).
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Redox and Acid–Base Chemistry of 7,7,8,8-Tetracyanoquinodimethane, 7,7,8,8-Tetracyanoquinodimethane Radical Anion, 7,7,8,8-Tetracyanoquinodimethane Dianion, and Dihydro-7,7,8,8-Tetracyanoquinodimethane in Acetonitrile
Analytical chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
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redox and acid base chemistry of 7 7 8 8 Tetracyanoquinodimethane 7 7 8 8 Tetracyanoquinodimethane radical anion 7 7 8 8 Tetracyanoquinodimethane dianion and dihydro 7 7 8 8 Tetracyanoquinodimethane in acetonitrile
Analytical Chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
Alan M. Bond - One of the best experts on this subject based on the ideXlab platform.
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role of water in the dynamic disproportionation of zn based tcnq f 4 coordination polymers tcnq Tetracyanoquinodimethane
Inorganic Chemistry, 2014Co-Authors: Ayman Nafady, Alan M. Bond, Naomi L Haworth, Lisandra L. MartinAbstract:Intriguingly, coordination polymers containing TCNQ2– and TCNQF42– (TCNQ = 7,7,8,8-Tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane, both designated as TCNQ(F4)2–) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN2– revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN2+. Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– ⇌ TCNQ(F4)MeCN + TCNQ(F4)MeCN2– is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10–10; TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN2+ + 2 TCNQ(F4)MeCN•– ⇌ ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble Z...
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identification of tcnqf4 redox levels using spectroscopic and electrochemical fingerprints tcnqf4 2 3 5 6 tetrafluoro 7 7 8 8 Tetracyanoquinodimethane
Inorganica Chimica Acta, 2013Co-Authors: Alan M. Bond, Lisandra L. MartinAbstract:Abstract Solution and solid state methods for the identification of TCNQF 4 , TCNQF 4 − and TCNQF 4 2 − redox levels (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) are described. Solution phase UV–Vis spectroscopy and electrochemistry can be used for both qualitative and quantitative determinations, while infrared and Raman spectroscopies are very powerful for solid state identification. Analogous strategies can also be applied to other TCNQ derivatives (TCNQ = 7,7,8,8-Tetracyanoquinodimethane).
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Identification of TCNQF4 redox levels using spectroscopic and electrochemical fingerprints (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane)
Inorganica Chimica Acta, 2013Co-Authors: Alan M. Bond, Lisandra L. MartinAbstract:Abstract Solution and solid state methods for the identification of TCNQF 4 , TCNQF 4 − and TCNQF 4 2 − redox levels (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) are described. Solution phase UV–Vis spectroscopy and electrochemistry can be used for both qualitative and quantitative determinations, while infrared and Raman spectroscopies are very powerful for solid state identification. Analogous strategies can also be applied to other TCNQ derivatives (TCNQ = 7,7,8,8-Tetracyanoquinodimethane).
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Redox and Acid–Base Chemistry of 7,7,8,8-Tetracyanoquinodimethane, 7,7,8,8-Tetracyanoquinodimethane Radical Anion, 7,7,8,8-Tetracyanoquinodimethane Dianion, and Dihydro-7,7,8,8-Tetracyanoquinodimethane in Acetonitrile
Analytical chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
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redox and acid base chemistry of 7 7 8 8 Tetracyanoquinodimethane 7 7 8 8 Tetracyanoquinodimethane radical anion 7 7 8 8 Tetracyanoquinodimethane dianion and dihydro 7 7 8 8 Tetracyanoquinodimethane in acetonitrile
Analytical Chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
Ayman Nafady - One of the best experts on this subject based on the ideXlab platform.
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role of water in the dynamic disproportionation of zn based tcnq f 4 coordination polymers tcnq Tetracyanoquinodimethane
Inorganic Chemistry, 2014Co-Authors: Ayman Nafady, Alan M. Bond, Naomi L Haworth, Lisandra L. MartinAbstract:Intriguingly, coordination polymers containing TCNQ2– and TCNQF42– (TCNQ = 7,7,8,8-Tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane, both designated as TCNQ(F4)2–) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN2– revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN2+. Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– ⇌ TCNQ(F4)MeCN + TCNQ(F4)MeCN2– is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10–10; TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN2+ + 2 TCNQ(F4)MeCN•– ⇌ ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble Z...
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Redox and Acid–Base Chemistry of 7,7,8,8-Tetracyanoquinodimethane, 7,7,8,8-Tetracyanoquinodimethane Radical Anion, 7,7,8,8-Tetracyanoquinodimethane Dianion, and Dihydro-7,7,8,8-Tetracyanoquinodimethane in Acetonitrile
Analytical chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
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redox and acid base chemistry of 7 7 8 8 Tetracyanoquinodimethane 7 7 8 8 Tetracyanoquinodimethane radical anion 7 7 8 8 Tetracyanoquinodimethane dianion and dihydro 7 7 8 8 Tetracyanoquinodimethane in acetonitrile
Analytical Chemistry, 2012Co-Authors: Ayman Nafady, Alan M. Bond, Lisandra L. MartinAbstract:The chemistry and electrochemistry of TCNQ (7,7,8,8-Tetracyanoquinodimethane), TCNQ•–, TCNQ2–, and H2TCNQ in acetonitrile (0.1 M Bu4NPF6) solution containing trifluoroacetic acid (TFA) has been studied by transient and steady-state voltammetric methods with the interrelationship between the redox and the acid–base chemistry being supported by simulations of the cyclic voltammograms. In the absence of acid, TCNQ and its anions undergo two electrochemically and chemically reversible one-electron processes. However, in the presence of TFA, the voltammetry is considerably more complex. The TCNQ2– dianion is protonated to form HTCNQ–, which is oxidized to HTCNQ•, and H2TCNQ which is electroinactive over the potential range of −1.0 to +1.0 V versus Ag/Ag+. The monoreduced TCNQ•– radical anion is weakly protonated to give HTCNQ•, which disproportionates to TCNQ and H2TCNQ. In acetonitrile, H2TCNQ deprotonates slowly, whereas in N,N-dimethylformamide or tetrahydrofuran, rapid deprotonation occurs to yield HTCNQ– ...
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detailed electrochemical analysis of the redox chemistry of tetrafluoroTetracyanoquinodimethane tcnqf4 the radical anion tcnqf4 and the dianion tcnqf4 2 in the presence of trifluoroacetic acid
Analytical Chemistry, 2011Co-Authors: Ayman Nafady, Lisandra L. Martin, Alan M. BondAbstract:The electrochemistry of 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane (TCNQF4), [TCNQF4]•–, and [TCNQF4]2– have been studied in acetonitrile (0.1 M [Bu4N][ClO4]). Transient and steady-state ...
Anthony P. O'mullane - One of the best experts on this subject based on the ideXlab platform.
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Tetrathiafulvalene–7,7,8,8-Tetracyanoquinodimethane and Tetrathiafulvalene–2,3,5,6-Tetrafluoro-7,7,8,8-Tetracyanoquinodimethane Organic Charge-Transfer Complexes: Reusable Catalysts for Electron-Transfer Reactions
ChemCatChem, 2016Co-Authors: Faegheh Hoshyargar, Anthony P. O'mullaneAbstract:The application of organic charge-transfer complexes such as TTF-TCNQ (TTF=tetrathiafulvalene, TCNQ=7,7,8,8-Tetracyanoquinodimethane) is well known in the area of organic electronics. However, the applicability of this material and its derivatives has not been explored for catalytic reactions. Herein, we report on the catalytic properties of both TTF-TCNQ and the significantly less-known fluorinated analogue TTF-TCNQF4 (TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane). The model reaction of ferricyanide ion reduction by thiosulfate ions was chosen, for which it was found that both materials were indeed catalytically active. Significantly, the fluorinated TCNQF4 analogue showed considerably higher catalytic activity than TTF-TCNQ. In addition, TTF-TCNQF4 was found to be highly stable under the catalytic conditions and could be recovered and reused without any loss in performance for at least 10 catalytic cycles. This work opens up new avenues for investigating these types of materials for catalytic reactions.
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Electrochemical formation of porous copper 7,7,8,8-Tetracyanoquinodimethane and copper 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane honeycomb surfaces with superhydrophobic properties
Electrochimica Acta, 2013Co-Authors: Manika Mahajan, Suresh K. Bhargava, Anthony P. O'mullaneAbstract:The electrochemical formation of highly porous CuTCNQ (TCNQ = 7,7,8,8-Tetracyanoquinodimethane) and CuTCNQF4 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) materials was undertaken via the spontaneous redox reaction between a porous copper template, created using a hydrogen bubbling template technique, and an acetonitrile solution containing TCNQ or TCNQF4. It was found that activation of the surface via vigorous hydrogen evolution that occurs during porous copper deposition and TCNQ mass transport being hindered through the porous network of the copper template influenced the growth of CuTCNQ and CuTCNQF4. This approach resulted in the fabrication of a honeycomb layered type structure where the internal walls consist of very fine crystalline needles or spikes. This combination of microscopic and nanoscopic roughness was found to be extremely beneficial for anti-wetting properties where superhydrophobic materials with contact angles as high as 177° were created. Given that CuTCNQ and CuTCNQF4 have shown potential as molecular based electronic materials in the area of switching and field emission, the creation of a surface that is moisture resistant may be of applied interest.
Tamotsu Inabe - One of the best experts on this subject based on the ideXlab platform.
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Charge Carrier Doping into the Peierls Insulator of the TCNQ Anion Radical Salt (TCNQ = 7,7,8,8-Tetracyanoquinodimethane)
The Journal of Physical Chemistry C, 2016Co-Authors: Hiroyuki Kubota, Yukihiro Takahashi, Hiroyuki Hasegawa, Takuro Shimada, Jun Harada, Tamotsu InabeAbstract:Hole-doping into K–TCNQ (TCNQ = 7,7,8,8-Tetracyanoquinodimethane) crystals with segregated TCNQ anion radical columns with dimeric deformation (Peierls state) has been performed by a contact doping method using F4TCNQ (F4TCNQ = 2,3,5,6-tetrafluoro-7,7,8,8-Tetracyanoquinodimethane) crystals or powder. The sheet resistance of the K–TCNQ surface has been found to decrease by the F4TCNQ contact. Formation of K–F4TCNQ nanocrystals at the contact interface has been observed, but conductive AFM images indicate that current paths form along the hole-doped K–TCNQ surface. Interestingly, hole-doping into K–TCNQ suppresses the phase transition to the high-temperature phase (Mott insulator). This is considered to result from the energy gain by the delocalization of the doped carriers.
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What Happens at the Interface between TTF and TCNQ Crystals (TTF = Tetrathiafulvalene and TCNQ = 7,7,8,8-Tetracyanoquinodimethane)?
The Journal of Physical Chemistry C, 2011Co-Authors: Yukihiro Takahashi, Kei Hayakawa, Toshio Naito, Tamotsu InabeAbstract:The interface between tetrathiafulvalene (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ) crystals was prepared by treating a TCNQ single crystal surface with TTF powder. Optical measurements and ...
