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Electrochemically Directed Synthesis of Cu2(I)(TCNQF4(II-))(MeCN)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane): Voltammetry, Simulations, Bulk Electrolysis, Spectroscopy, Photoactivity, and X-ray Crystal Structure of the Cu2(I)(TCNQF4(II-))(EtCN)2 Analogue

Electrochemically Directed Synthesis of Cu2(I)(TCNQF4(II-))(MeCN)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane): Voltammetry, Simulations, Bulk Electrolysis, Spectroscopy, Photoactivity, and X-ray Crystal Structure of the Cu2(I)(TCNQF4(II-))(EtCN)2 Analogue

Thanh H Le, Ayman Nafady, Nguyen T Vo, Robert W Elliott, Timothy A Hudson, Richard Robson, Brendan F Abrahams, Lisandra L Martin, Alan M Bond

Inorg Chem. 2014 Mar 17;53(6):3230-42.

PMID: 24568268

Abstract:

The new compound Cu2(I)(TCNQF4(II-))(MeCN)2 (TCNQF4(2-) = dianion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) has been synthesized by electrochemically directed synthesis involving reduction of TCNQF4 to TCNQF4(2-) in acetonitrile containing [Cu(MeCN)4](+)(MeCN) and 0.1 M Bu4NPF6. In one scenario, TCNQF4(2-) is quantitatively formed by reductive electrolysis of TCNQF4 followed by addition of [Cu(MeCN)4](+) to form the Cu2(I)(TCNQF4(II-))(MeCN)2 coordination polymer. In a second scenario, TCNQF4 is reduced in situ at the electrode surface to TCNQF4(2-), followed by reaction with the [Cu(MeCN)4](+) present in the solution, to electrocrystallize Cu2(I)(TCNQF4(II-))(MeCN)2. Two distinct phases of Cu2(I)(TCNQF4(II-))(MeCN)2 are formed in this scenario; the kinetically favored form being rapidly converted to the thermodynamically favored Cu2(I)(TCNQF4(II-))(MeCN)2. The postulated mechanism is supported by simulations. The known compound Cu(I)TCNQF4(I-) also has been isolated by one electron reduction of TCNQF4 and reaction with [Cu(MeCN)4](+). The solubility of both TCNQF4(2-)- and TCNQF4(•-)-derived solids indicates that the higher solubility of Cu(I)TCNQF4(I-) prevents its precipitation, and thus Cu2(I)(TCNQF4(II-))(MeCN)2 is formed. UV-visible and vibrational spectroscopies were used to characterize the materials. Cu2(I)(TCNQF4(II-))(MeCN)2 can be photochemically transformed to Cu(I)TCNQF4(I-) and Cu(0). Scanning electron microscopy images reveal that Cu(I)TCNQF4(I-) and Cu2(I)(TCNQF4(II-))(MeCN)2 are electrocrystallized with distinctly different morphologies. Thermogravimetric and elemental analysis data confirm the presence of CH3CN, and single-crystal X-ray diffraction data for the Cu2(I)(TCNQF4(II-))(EtCN)2 analogue shows that this compound is structurally related to Cu2(I)(TCNQF4(II-))(MeCN)2.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP29261334	2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane		29261-33-4	Price

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