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

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 on...

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Veröffentlicht in:Inorganic chemistry 2014-03, Vol.53 (6), p.3230-3242
Hauptverfasser: Le, Thanh H, Nafady, Ayman, Vo, Nguyen T, Elliott, Robert W, Hudson, Timothy A, Robson, Richard, Abrahams, Brendan F, Martin, Lisandra L, Bond, Alan M
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container_end_page 3242
container_issue 6
container_start_page 3230
container_title Inorganic chemistry
container_volume 53
creator Le, Thanh H
Nafady, Ayman
Vo, Nguyen T
Elliott, Robert W
Hudson, Timothy A
Robson, Richard
Abrahams, Brendan F
Martin, Lisandra L
Bond, Alan M
description 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.
doi_str_mv 10.1021/ic500225v
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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.</description><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic500225v</identifier><identifier>PMID: 24568268</identifier><language>eng</language><publisher>United States</publisher><ispartof>Inorganic chemistry, 2014-03, Vol.53 (6), p.3230-3242</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24568268$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Le, Thanh H</creatorcontrib><creatorcontrib>Nafady, Ayman</creatorcontrib><creatorcontrib>Vo, Nguyen T</creatorcontrib><creatorcontrib>Elliott, Robert W</creatorcontrib><creatorcontrib>Hudson, Timothy A</creatorcontrib><creatorcontrib>Robson, Richard</creatorcontrib><creatorcontrib>Abrahams, Brendan F</creatorcontrib><creatorcontrib>Martin, Lisandra L</creatorcontrib><creatorcontrib>Bond, Alan M</creatorcontrib><title>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</title><title>Inorganic chemistry</title><addtitle>Inorg Chem</addtitle><description>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.</description><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNptUU1rFEEQHQUxMfEgeJY-zsBM7I_p-Qh4kGGjCzFBiJDb0l_jtvZMj_2xMP_eNrveUpfivXoU71Vl2TsErxDE6KMWFEKM6eFldo4ohhVF8PEse-P9LwhhT-rmdXaGa9p0uOnOX7zfGCWCs2KvJi2YMSuQ2iVKSeDXOeyV1x7YEQwR59sifxjuvt_U-XZbFUX-TQ13BQYnEnwCuCQlLZsqqODYaKJ1tmrLtuzK7siJlc32T9SzlXpSYc9mVVyDgzWBTQm7tQReT9GwoO3sS8Cj-Q3U0aJZk5U0X56QF3ZJ6mVvg2Ui6IMOCbJZgsfKsRUIt_rADPDBRRGiU_9CpDjPBtmEpyBsZsb-jOoyezUy49XbU7_IftxsHoav1e39l-3w-bZaEG5C1RPZobbneOQNJxSrse3HBkKCR9LKRCpS1x0lqVgt-UhpD7lAXSsZZ0pycpHlx72LS0dRPuwm7YUyJp3FRr9DFHY1hrRrkvTDSRr5pORucXpibt39_yT5C3k_nFM</recordid><startdate>20140317</startdate><enddate>20140317</enddate><creator>Le, Thanh H</creator><creator>Nafady, Ayman</creator><creator>Vo, Nguyen T</creator><creator>Elliott, Robert W</creator><creator>Hudson, Timothy A</creator><creator>Robson, Richard</creator><creator>Abrahams, Brendan F</creator><creator>Martin, Lisandra L</creator><creator>Bond, Alan M</creator><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20140317</creationdate><title>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</title><author>Le, Thanh H ; Nafady, Ayman ; Vo, Nguyen T ; Elliott, Robert W ; Hudson, Timothy A ; Robson, Richard ; Abrahams, Brendan F ; Martin, Lisandra L ; Bond, Alan M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p126t-93d8179b2fb6b352ef79f60032f37dfb6e344853333a4dbf5590bc187dabaedb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Le, Thanh H</creatorcontrib><creatorcontrib>Nafady, Ayman</creatorcontrib><creatorcontrib>Vo, Nguyen T</creatorcontrib><creatorcontrib>Elliott, Robert W</creatorcontrib><creatorcontrib>Hudson, Timothy A</creatorcontrib><creatorcontrib>Robson, Richard</creatorcontrib><creatorcontrib>Abrahams, Brendan F</creatorcontrib><creatorcontrib>Martin, Lisandra L</creatorcontrib><creatorcontrib>Bond, Alan M</creatorcontrib><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Le, Thanh H</au><au>Nafady, Ayman</au><au>Vo, Nguyen T</au><au>Elliott, Robert W</au><au>Hudson, Timothy A</au><au>Robson, Richard</au><au>Abrahams, Brendan F</au><au>Martin, Lisandra L</au><au>Bond, Alan M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>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</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg Chem</addtitle><date>2014-03-17</date><risdate>2014</risdate><volume>53</volume><issue>6</issue><spage>3230</spage><epage>3242</epage><pages>3230-3242</pages><eissn>1520-510X</eissn><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.</abstract><cop>United States</cop><pmid>24568268</pmid><doi>10.1021/ic500225v</doi><tpages>13</tpages></addata></record>
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title 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
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