Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Tetrathiafulvalene: Difference between pages

{{Short description|Organosulfuric compound with formula C6H4S4}}

|Watchedfields = changed

|verifiedrevid = 470605170

|Name = Tetrathiafulvalene

|ImageFile = Tetrathiafulvalene.svg

|ImageAlt = Skeletal formula of tetrathiafulvalene

|ImageFile1 = Tetrathiafulvalene-3D-balls.png

|ImageAlt1 = Ball-and-stick model of the tetrathiafulvalene molecule

|ImageFile2 = Sample of TTF.jpg

|PIN = 2,2′-Bi(1,3-dithiolylidene)

|OtherNames = Δ2,2-Bi-1,3-dithiole

|Section1={{Chembox Identifiers

|CASNo_Ref = {{cascite|correct|CAS}}

|CASNo = 31366-25-3

|Beilstein = 1282106

|ChEBI_Ref = {{ebicite|correct|EBI}}

|ChEBI = 52444

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 89848

| EC_number = 250-593-7

|PubChem = 99451

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = HY1EN16W9T

|InChI = 1/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H

|InChIKey = FHCPAXDKURNIOZ-UHFFFAOYAZ

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/C6H4S4/c1-2-8-5(7-1)6-9-3-4-10-6/h1-4H

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = FHCPAXDKURNIOZ-UHFFFAOYSA-N

|SMILES = S1C=CSC1=C2SC=CS2

|Section2={{Chembox Properties

|C=6|H=4|S=4

|Appearance = Yellow solid

|Solvent = organic solvents

|Solubility = Insoluble

|SolubleOther = Soluble{{vague|date=December 2016}}

|MeltingPtC = 116 to 119

|BoilingPt = Decomposes

}}

|Section3={{Chembox Structure

| Dipole = 0 [[Debye|D]]

}}

|Section7={{Chembox Hazards

|MainHazards = combustible

| 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>

| GHSPictograms = {{GHS07}}

| GHSSignalWord = Warning

| HPhrases = {{H-phrases|317}}

| PPhrases = {{P-phrases|261|280|302+352|333+313|363|501}}

}}

|Section8={{Chembox Related

| OtherCompounds = {{ubl|[[TCNQ]]|[[Thiophene]]|[[Tetracyanoethylene]]}}

}}

}}

'''Tetrathiafulvalene''' ('''TTF''') is an [[organosulfur compound]] with the [[chemical formula|formula]] ({{chem2|C3H2S2)2}}. Studies on this [[heterocyclic]] compound contributed to the development of [[molecular electronics]]. TTF is related to the hydrocarbon [[fulvalene]], {{chem2|(C5H4)2}}, by replacement of four [[Methine group|CH groups]] 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 = [[Chemical Reviews]] | year = 2004 | volume = 104 | pages = 4891–4945 | doi = 10.1021/cr030666m | pmid = 15535637 | issue = 11}}</ref>

==Preparation==

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 [[1,3-Dithiole|1,3-dithiole]]-2-thion or the related 1,3-dithiole-2-ones. For TTF itself, the synthesis begins with the [[Cyclic compound|cyclic]] [[trithiocarbonate]] {{chem2|H2C2S2C\dS}} ([[1,3-dithiole-2-thione]]), which is [[Methylation|''S''-methylated]] 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 = [[Inorg. Synth.]] | year = 1979 | volume = 19 | pages = 27–30 | doi = 10.1002/9780470132500.ch7 | isbn = 978-0-470-13250-0}}</ref>

:{{chem2|H2C2S2CH(SCH3) + [[Fluoroboric acid|H[BF4] ]] → [H2C2S2CH]+[BF4]− + [[Methanethiol|CH3SH]]}}

:{{chem2|2 [H2C2S2CH]+[BF4]− + 2 [[Triethylamine|N(CH2CH3)3]] → (H2C2S2C)2 + 2 [NH(CH2CH3)3]+[BF4]−}}

==Redox properties==

Bulk TTF itself has unremarkable electrical properties. Distinctive properties are, however, associated with salts of its [[oxidized]] derivatives, such as salts derived from {{chem2|TTF+}}.

The high electrical conductivity of TTF salts can be attributed to the following features of TTF:

*its planarity, which allows [[Pi-Stacking (chemistry)|π-π stacking]] of its oxidized derivatives,

*its high symmetry, which promotes [[Delocalized electron|charge delocalization]], thereby minimizing [[coulombic]] repulsions, and

*its ability to undergo oxidation at mild potentials to give a stable [[radical cation]]. [[Electrochemistry|Electrochemical]] measurements show that TTF can be oxidized twice reversibly:

:{{chem2|TTF → TTF+ + e-}} (''E'' = 0.34 [[Volt (unit)|V]])

:{{chem2|TTF+ → TTF(2+) + e-}} (''E'' = 0.78 V, vs. [[Silver|Ag]]/[[Silver(I) chloride|AgCl]] in [[Acetonitrile|{{chem2|CH3CN}}]] solution)

Each dithiolylidene ring in TTF has 7π electrons: 2 for each sulfur atom, 1 for each [[Orbital hybridisation|sp²]] carbon atom. Thus, oxidation converts each ring to an [[aromatic]] 6π-electron configuration, consequently leaving the central double bond essentially a single bond, as all π-electrons occupy ring orbitals.

==History==

[[File:SegStackEdgeOnHMTFCQ.jpg|thumb|left|Edge-on view of portion of crystal structure of hexamethyleneTTF/TCNQ charge transfer salt, highlighting the segregated stacking.<ref>{{cite journal|author1=D. Chasseau|author2=G. Comberton|author3=J. Gaultier|author4=C. Hauw|journal=Acta Crystallographica Section B|title=Réexamen de la structure du complexe hexaméthylène-tétrathiafulvalène-tétracyanoquinodiméthane|year=1978| volume=34|issue=2|page=689|doi=10.1107/S0567740878003830|doi-access=free|bibcode=1978AcCrB..34..689C }}</ref>]]

The salt {{chem|[TTF|+|]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 = [[J. Am. Chem. Soc.]]| year = 1972 | volume = 94 | pages = 670–672 | doi = 10.1021/ja00757a079 | issue = 2}}</ref> Subsequently, the charge-transfer salt [TTF][[TCNQ]] was shown to be a narrow [[band gap]] 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 = [[J. Am. Chem. Soc.]] | year = 1973 | volume = 95 | pages = 948–949 | doi = 10.1021/ja00784a066 | issue = 3}}</ref> [[X-ray diffraction]] studies of [TTF][TCNQ] 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 [[anisotropic]] [[electrical conductivity]]. Since these early discoveries, numerous analogues of TTF have been prepared. Well studied analogues include tetramethyltetrathiafulvalene (Me₄TTF), tetramethylselenafulvalenes (TMTSFs), and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, CAS [66946-48-3]).<ref>{{OrgSynth | author = Larsen, J.; Lenoir, C. | title = <nowiki>2,2'-Bi-5,6-Dihydro-1,3-Dithiolo[4,5-b][1,4]dithiinylidene (BEDT-TTF)</nowiki> | collvol = 9 | collvolpages = 72 | prep = cv9p0072 | year = 1998}}</ref> Several tetramethyltetrathiafulvalene salts (called '''Fabre salts''') are of some relevance as [[organic superconductor]]s.

==See also==

* [[Bechgaard salt]]

==References==

{{Reflist}}

==Further reading==

* {{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 = [[Chemical Reviews]] | year = 2004 | volume = 104 | pages = 5289–5317 | doi = 10.1021/cr030663+| pmid = 15535651 | issue = 11}}

* {{cite journal |author1=Iyoda, M |author2=Hasegawa, M |author3=Miyake, Y | title = Bi-TTF, Bis-TTF, and Related TTF Oligomers | journal = [[Chemical Reviews]] | year = 2004 | volume = 104 | pages = 5085–5113 | doi = 10.1021/cr030651o | pmid = 15535643 | issue = 11}}

* {{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 = [[Chemical Society Reviews]] | year = 2005 | volume = 34 | pages = 69–98 | doi = 10.1039/b316392j | pmid = 15643491 | issue = 1}}

* {{cite journal |author1=Gorgues, Alain |author2=Hudhomme, Pietrick |author3=Salle, Marc. | title = Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes | journal = [[Chemical Reviews]] | year = 2004 | volume = 104 | pages = 5151–5184 | doi = 10.1021/cr0306485 | pmid = 15535646 | issue = 11}}

* [https://www.chemeo.com/cid/10-573-4/Tetrathiafulvalene Physical properties of Tetrathiafulvalene] from the literature.

*{{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 }}

[[Category:Molecular electronics]]

[[Category:Organic semiconductors]]

[[Category:Dithioles]]