| Revision as of 12:47, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,044 edits Saving copy of the {{chembox}} taken from revid 467571876 of page Tetrathiafulvalene for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 22:47, 27 March 2024 edit IznoRepeat (talk | contribs)Extended confirmed users50,076 editsm cleaning Category:CS1 maint: multiple names: authors list (Jr), genfixesTag: AWB |
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{{Short description|Organosulfuric compound with formula C6H4S4}} |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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|Watchedfields = changed |
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| verifiedrevid = 444221564 |
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|verifiedrevid = 470605170 |
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| Name = Tetrathiafulvalene |
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| ImageFile = Tetrathiafulvalene.svg |
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|Name = Tetrathiafulvalene |
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|ImageFile = Tetrathiafulvalene.svg |
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| IUPACName = 2,2’-bis(1,3-dithiolylidene) |
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|ImageAlt = Skeletal formula of tetrathiafulvalene |
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| OtherNames = Δ2,2-bi-1,3-dithiole |
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|ImageFile1 = Tetrathiafulvalene-3D-balls.png |
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| Section1 = {{Chembox Identifiers |
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|ImageAlt1 = Ball-and-stick model of the tetrathiafulvalene molecule |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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|ImageFile2 = Sample of TTF.jpg |
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| ChEBI = 52444 |
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|PIN = 2,2′-Bi(1,3-dithiolylidene) |
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| SMILES = C1=CSC(=C2SC=CS2)S1 |
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|OtherNames = Δ2,2-Bi-1,3-dithiole |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID = 89848 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = 99451 |
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|CASNo = 31366-25-3 |
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| InChI = 1/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H |
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|Beilstein = 1282106 |
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| InChIKey = FHCPAXDKURNIOZ-UHFFFAOYAZ |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|ChEBI_Ref = {{ebicite|correct|EBI}} |
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|ChEBI = 52444 |
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| StdInChI = 1S/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID = 89848 |
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| StdInChIKey = FHCPAXDKURNIOZ-UHFFFAOYSA-N |
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| EC_number = 250-593-7 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|PubChem = 99451 |
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| CASNo = 31366-25-3 |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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| RTECS = |
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|UNII = HY1EN16W9T |
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}} |
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|InChI = 1/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H |
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| Section2 = {{Chembox Properties |
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|InChIKey = FHCPAXDKURNIOZ-UHFFFAOYAZ |
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| Formula = C<sub>6</sub>H<sub>4</sub>S<sub>4</sub> |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| MolarMass = 204.36 g/mol |
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|StdInChI = 1S/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H |
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| Appearance = yellow solid |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| Density = ? g/cm<sup>3</sup> |
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|StdInChIKey = FHCPAXDKURNIOZ-UHFFFAOYSA-N |
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| Solvent = other solvents |
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|SMILES = S1C=CSC1=C2SC=CS2 |
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| SolubleOther = insoluble in water,<br />soluble in organic<br />solvents |
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| MeltingPt = 116-119 °C |
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| BoilingPt = decomp. |
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}}<!-- |
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| geometry |
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| planar (D<sub>2h</sub>) |
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--> |
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| Section3 = {{Chembox Structure |
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| CrystalStruct = |
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| Dipole = 0 ] |
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}} |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = |
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| MainHazards = combustible |
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| RPhrases = 43 |
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| SPhrases = 36/37 |
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}} |
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| Section8 = {{Chembox Related |
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| OtherCpds = ],<br />] |
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}} |
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}} |
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}} |
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|Section2={{Chembox Properties |
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|C=6|H=4|S=4 |
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|Appearance = Yellow solid |
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|Solvent = organic solvents |
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|Solubility = Insoluble |
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|SolubleOther = Soluble{{vague|date=December 2016}} |
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|MeltingPtC = 116 to 119 |
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|BoilingPt = Decomposes |
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}} |
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|Section3={{Chembox Structure |
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| Dipole = 0 ] |
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}} |
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|Section7={{Chembox Hazards |
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|MainHazards = combustible |
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| Hazards_ref=<ref>{{cite web |title=Tetrathiafulvalene |url=https://pubchem.ncbi.nlm.nih.gov/compound/99451#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en}}</ref> |
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| GHSPictograms = {{GHS07}} |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|317}} |
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| PPhrases = {{P-phrases|261|280|302+352|333+313|363|501}} |
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}} |
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|Section8={{Chembox Related |
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| OtherCompounds = {{ubl|]|]|]}} |
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}} |
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}} |
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'''Tetrathiafulvalene''' ('''TTF''') is an ] with the ] ({{chem2|C3H2S2)2}}. Studies on this ] compound contributed to the development of ]. TTF is related to the hydrocarbon ], {{chem2|(C5H4)2}}, by replacement of four ] with sulfur atoms. Over 10,000 scientific publications discuss TTF and its derivatives.<ref name=Bendikov>{{cite journal |author1=Bendikov, M |author2=Wudl, F |author3=Perepichka, D F |author3-link=Dmitrii Perepichka | title = Tetrathiafulvalenes, Oligoacenenes, and Their Buckminsterfullerene Derivatives: The Brick and Mortar of Organic Electronics | journal = ] | year = 2004 | volume = 104 | pages = 4891–4945 | doi = 10.1021/cr030666m | pmid = 15535637 | issue = 11}}</ref> |
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==Preparation== |
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The high level of interest in TTFs has spawned the development of many syntheses of TTF and its analogues.<ref name=Bendikov/> Most preparations entail the coupling of cyclic {{chem2|C3S2}} building blocks such as ]-2-thion or the related 1,3-dithiole-2-ones. For TTF itself, the synthesis begins with the ] ] {{chem2|H2C2S2C\dS}} (]), which is ] and then reduced to give {{chem2|H2C2S2CH(SCH3)}} (1,3-dithiole-2-yl methyl thioether), which is treated as follows:<ref>{{cite book |author1=Wudl, F. |author2=Kaplan, M. L. |title=Inorganic Syntheses |chapter=2,2′-Bi-L,3-Dithiolylidene (Tetrathiafulvalene, TTF) and its Radical Cation Salts | journal = ] | year = 1979 | volume = 19 | pages = 27–30 | doi = 10.1002/9780470132500.ch7 | isbn = 978-0-470-13250-0}}</ref> |
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:{{chem2|H2C2S2CH(SCH3) + ]] → +− + ]}} |
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:{{chem2|2 +− + 2 ] → (H2C2S2C)2 + 2 +−}} |
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==Redox properties== |
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Bulk TTF itself has unremarkable electrical properties. Distinctive properties are, however, associated with salts of its ] derivatives, such as salts derived from {{chem2|TTF+}}. |
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The high electrical conductivity of TTF salts can be attributed to the following features of TTF: |
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*its planarity, which allows ] of its oxidized derivatives, |
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*its high symmetry, which promotes ], thereby minimizing ] repulsions, and |
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*its ability to undergo oxidation at mild potentials to give a stable ]. ] measurements show that TTF can be oxidized twice reversibly: |
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:{{chem2|TTF → TTF+ + e-}} (''E'' = 0.34 ]) |
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:{{chem2|TTF+ → TTF(2+) + e-}} (''E'' = 0.78 V, vs. ]/] in ] solution) |
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Each dithiolylidene ring in TTF has 7π electrons: 2 for each sulfur atom, 1 for each ] carbon atom. Thus, oxidation converts each ring to an ] 6π-electron configuration, consequently leaving the central double bond essentially a single bond, as all π-electrons occupy ring orbitals. |
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==History== |
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] |
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The salt {{chem|Cl|-}} was reported to be a semiconductor in 1972.<ref>{{cite journal |author1=Wudl, F. |author2=Wobschall, D. |author3=Hufnagel, E. J. | title = Electrical Conductivity by the Bis(1,3-dithiole)-bis(1,3-dithiolium) System | journal = ]| year = 1972 | volume = 94 | pages = 670–672 | doi = 10.1021/ja00757a079 | issue = 2}}</ref> Subsequently, the charge-transfer salt ] was shown to be a narrow ] semiconductor.<ref>{{cite journal |author1=Ferraris, J. |author2=Cowan, D. O. |author3=Walatka, V. V. Jr. |author4=Perlstein, J. H. | title = Electron transfer in a new highly conducting donor-acceptor complex | journal = ] | year = 1973 | volume = 95 | pages = 948–949 | doi = 10.1021/ja00784a066 | issue = 3}}</ref> ] studies of revealed stacks of partially oxidized TTF molecules adjacent to anionic stacks of TCNQ molecules. This "segregated stack" motif was unexpected and is responsible for the distinctive electrical properties, i.e. high and ] ]. Since these early discoveries, numerous analogues of TTF have been prepared. Well studied analogues include tetramethyltetrathiafulvalene (Me<sub>4</sub>TTF), tetramethylselenafulvalenes (TMTSFs), and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, CAS ).<ref>{{OrgSynth | author = Larsen, J.; Lenoir, C. | title = <nowiki>2,2'-Bi-5,6-Dihydro-1,3-Dithiolodithiinylidene (BEDT-TTF)</nowiki> | collvol = 9 | collvolpages = 72 | prep = cv9p0072 | year = 1998}}</ref> Several tetramethyltetrathiafulvalene salts (called '''Fabre salts''') are of some relevance as ]s. |
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==See also== |
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* ] |
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==References== |
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{{Reflist}} |
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==Further reading== |
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* {{cite journal | author = Rovira, C. | title = Bis(ethylenethio)tetrathiafulvalene (BET-TTF) and Related Dissymmetrical Electron Donors: From the Molecule to Functional Molecular Materials and Devices (OFETs) | journal = ] | year = 2004 | volume = 104 | pages = 5289–5317 | doi = 10.1021/cr030663+| pmid = 15535651 | issue = 11}} |
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* {{cite journal |author1=Iyoda, M |author2=Hasegawa, M |author3=Miyake, Y | title = Bi-TTF, Bis-TTF, and Related TTF Oligomers | journal = ] | year = 2004 | volume = 104 | pages = 5085–5113 | doi = 10.1021/cr030651o | pmid = 15535643 | issue = 11}} |
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* {{cite journal |author1=Frere, P. |author2=Skabara, P. J. | title = Salts of Extended Tetrathiafulvalene analogues: relationships Between Molecular Structure, Electrochemical Properties and Solid State Organization | journal = ] | year = 2005 | volume = 34 | pages = 69–98 | doi = 10.1039/b316392j | pmid = 15643491 | issue = 1}} |
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* {{cite journal |author1=Gorgues, Alain |author2=Hudhomme, Pietrick |author3=Salle, Marc. | title = Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes | journal = ] | year = 2004 | volume = 104 | pages = 5151–5184 | doi = 10.1021/cr0306485 | pmid = 15535646 | issue = 11}} |
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* from the literature. |
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*{{cite journal |doi=10.1002/1521-3773(20010417)40:8<1372::aid-anie1372>3.0.co;2-i |title=New Concepts in Tetrathiafulvalene Chemistry |date=2001 |last1=Segura |first1=José L. |last2=Martín |first2=Nazario |journal=Angewandte Chemie International Edition |volume=40 |issue=8 |pages=1372–1409 |pmid=11317287 }} |
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