Tetrathiafulvalene (TTF) is an organosulfur compound with the formula (C3H2S2)2. Studies on this heterocyclic compound contributed to the development of molecular electronics. TTF is related to the hydrocarbon fulvalene, (C5H4)2, by replacement of four CH groups with sulfur atoms. Over 10,000 scientific publications discuss TTF and its derivatives.[2]
The high level of interest in TTFs has spawned the development of many syntheses of TTF and its analogues.[2] Most preparations entail the coupling of cyclic C3S2 building blocks such as 1,3-dithiole-2-thion or the related 1,3-dithiole-2-ones. For TTF itself, the synthesis begins with the cyclictrithiocarbonateH2C2S2C=S (1,3-dithiole-2-thione), which is S-methylated and then reduced to give H2C2S2CH(SCH3) (1,3-dithiole-2-yl methyl thioether), which is treated as follows:[3]
Bulk TTF itself has unremarkable electrical properties. Distinctive properties are, however, associated with salts of its oxidized derivatives, such as salts derived from TTF+.
The high electrical conductivity of TTF salts can be attributed to the following features of TTF:
its planarity, which allows π-π stacking of its oxidized derivatives,
its ability to undergo oxidation at mild potentials to give a stable radical cation. Electrochemical measurements show that TTF can be oxidized twice reversibly:
TTF+ → TTF2+ + e− (E = 0.78 V, vs. Ag/AgCl in CH3CN solution)
Each dithiolylidene ring in TTF has 7π electrons: 2 for each sulfur atom, 1 for each 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.
Historyedit
Edge-on view of portion of crystal structure of hexamethyleneTTF/TCNQ charge transfer salt, highlighting the segregated stacking.[4]
The salt [TTF+ ]Cl− was reported to be a semiconductor in 1972.[5] Subsequently, the charge-transfer salt [TTF]TCNQ was shown to be a narrow band gap semiconductor.[6]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 anisotropicelectrical 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]).[7] Several tetramethyltetrathiafulvalene salts (called Fabre salts) are of some relevance as organic superconductors.
^ abBendikov, M; Wudl, F; Perepichka, D F (2004). "Tetrathiafulvalenes, Oligoacenenes, and Their Buckminsterfullerene Derivatives: The Brick and Mortar of Organic Electronics". Chemical Reviews. 104 (11): 4891–4945. doi:10.1021/cr030666m. PMID 15535637.
^Wudl, F.; Kaplan, M. L. (1979). "2,2′-Bi-L,3-Dithiolylidene (Tetrathiafulvalene, TTF) and its Radical Cation Salts". Inorganic Syntheses. Vol. 19. pp. 27–30. doi:10.1002/9780470132500.ch7. ISBN978-0-470-13250-0. {{cite book}}: |journal= ignored (help)
^D. Chasseau; G. Comberton; J. Gaultier; C. Hauw (1978). "Réexamen de la structure du complexe hexaméthylène-tétrathiafulvalène-tétracyanoquinodiméthane". Acta Crystallographica Section B. 34 (2): 689. Bibcode:1978AcCrB..34..689C. doi:10.1107/S0567740878003830.
^Wudl, F.; Wobschall, D.; Hufnagel, E. J. (1972). "Electrical Conductivity by the Bis(1,3-dithiole)-bis(1,3-dithiolium) System". J. Am. Chem. Soc.94 (2): 670–672. doi:10.1021/ja00757a079.
^Ferraris, J.; Cowan, D. O.; Walatka, V. V. Jr.; Perlstein, J. H. (1973). "Electron transfer in a new highly conducting donor-acceptor complex". J. Am. Chem. Soc.95 (3): 948–949. doi:10.1021/ja00784a066.
^Larsen, J.; Lenoir, C. (1998). "2,2'-Bi-5,6-Dihydro-1,3-Dithiolo[4,5-b][1,4]dithiinylidene (BEDT-TTF)". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 9, p. 72.
Further readingedit
Rovira, C. (2004). "Bis(ethylenethio)tetrathiafulvalene (BET-TTF) and Related Dissymmetrical Electron Donors: From the Molecule to Functional Molecular Materials and Devices (OFETs)". Chemical Reviews. 104 (11): 5289–5317. doi:10.1021/cr030663+. PMID 15535651.
Iyoda, M; Hasegawa, M; Miyake, Y (2004). "Bi-TTF, Bis-TTF, and Related TTF Oligomers". Chemical Reviews. 104 (11): 5085–5113. doi:10.1021/cr030651o. PMID 15535643.
Frere, P.; Skabara, P. J. (2005). "Salts of Extended Tetrathiafulvalene analogues: relationships Between Molecular Structure, Electrochemical Properties and Solid State Organization". Chemical Society Reviews. 34 (1): 69–98. doi:10.1039/b316392j. PMID 15643491.
Gorgues, Alain; Hudhomme, Pietrick; Salle, Marc. (2004). "Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes". Chemical Reviews. 104 (11): 5151–5184. doi:10.1021/cr0306485. PMID 15535646.
Physical properties of Tetrathiafulvalene from the literature.
Segura, José L.; Martín, Nazario (2001). "New Concepts in Tetrathiafulvalene Chemistry". Angewandte Chemie International Edition. 40 (8): 1372–1409. doi:10.1002/1521-3773(20010417)40:8<1372::aid-anie1372>3.0.co;2-i. PMID 11317287.
January 01, 1970
tetrathiafulvalene, organosulfur, compound, with, formula, c3h2s2, studies, this, heterocyclic, compound, contributed, development, molecular, electronics, related, hydrocarbon, fulvalene, c5h4, replacement, four, groups, with, sulfur, atoms, over, scientific,. Tetrathiafulvalene TTF is an organosulfur compound with the formula C3H2S2 2 Studies on this heterocyclic compound contributed to the development of molecular electronics TTF is related to the hydrocarbon fulvalene C5H4 2 by replacement of four CH groups with sulfur atoms Over 10 000 scientific publications discuss TTF and its derivatives 2 Tetrathiafulvalene Names Preferred IUPAC name 2 2 Bi 1 3 dithiolylidene Other names D2 2 Bi 1 3 dithiole Identifiers CAS Number 31366 25 3 Y 3D model JSmol Interactive image Beilstein Reference 1282106 ChEBI CHEBI 52444 Y ChemSpider 89848 Y ECHA InfoCard 100 045 979 EC Number 250 593 7 PubChem CID 99451 UNII HY1EN16W9T Y CompTox Dashboard EPA DTXSID6067620 InChI InChI 1S C6H4S4 c1 2 8 5 7 1 6 9 3 4 10 6 h1 4H YKey FHCPAXDKURNIOZ UHFFFAOYSA N YInChI 1 C6H4S4 c1 2 8 5 7 1 6 9 3 4 10 6 h1 4HKey FHCPAXDKURNIOZ UHFFFAOYAZ SMILES S1C CSC1 C2SC CS2 Properties Chemical formula C 6H 4S 4 Molar mass 204 34 g mol 1 Appearance Yellow solid Melting point 116 to 119 C 241 to 246 F 389 to 392 K Boiling point Decomposes Solubility in water Insoluble Solubility in organic solvents Soluble vague Structure Dipole moment 0 D Hazards 1 Occupational safety and health OHS OSH Main hazards combustible GHS labelling Pictograms Signal word Warning Hazard statements H317 Precautionary statements P261 P280 P302 P352 P333 P313 P363 P501 Related compounds Related compounds TCNQThiopheneTetracyanoethylene Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Contents 1 Preparation 2 Redox properties 3 History 4 See also 5 References 6 Further readingPreparation editThe high level of interest in TTFs has spawned the development of many syntheses of TTF and its analogues 2 Most preparations entail the coupling of cyclic C3S2 building blocks such as 1 3 dithiole 2 thion or the related 1 3 dithiole 2 ones For TTF itself the synthesis begins with the cyclic trithiocarbonate H2C2S2C S 1 3 dithiole 2 thione which is S methylated and then reduced to give H2C2S2CH SCH3 1 3 dithiole 2 yl methyl thioether which is treated as follows 3 H2C2S2CH SCH3 H BF4 H2C2S2CH BF4 CH3SH 2 H2C2S2CH BF4 2 N CH2CH3 3 H2C2S2C 2 2 NH CH2CH3 3 BF4 Redox properties editBulk TTF itself has unremarkable electrical properties Distinctive properties are however associated with salts of its oxidized derivatives such as salts derived from TTF The high electrical conductivity of TTF salts can be attributed to the following features of TTF its planarity which allows p p stacking of its oxidized derivatives its high symmetry which promotes charge delocalization thereby minimizing coulombic repulsions and its ability to undergo oxidation at mild potentials to give a stable radical cation Electrochemical measurements show that TTF can be oxidized twice reversibly TTF TTF e E 0 34 V TTF TTF2 e E 0 78 V vs Ag AgCl in CH3CN solution Each dithiolylidene ring in TTF has 7p electrons 2 for each sulfur atom 1 for each sp2 carbon atom Thus oxidation converts each ring to an aromatic 6p electron configuration consequently leaving the central double bond essentially a single bond as all p electrons occupy ring orbitals History edit nbsp Edge on view of portion of crystal structure of hexamethyleneTTF TCNQ charge transfer salt highlighting the segregated stacking 4 The salt TTF Cl was reported to be a semiconductor in 1972 5 Subsequently the charge transfer salt TTF TCNQ was shown to be a narrow band gap semiconductor 6 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 7 Several tetramethyltetrathiafulvalene salts called Fabre salts are of some relevance as organic superconductors See also editBechgaard saltReferences edit Tetrathiafulvalene pubchem ncbi nlm nih gov a b Bendikov M Wudl F Perepichka D F 2004 Tetrathiafulvalenes Oligoacenenes and Their Buckminsterfullerene Derivatives The Brick and Mortar of Organic Electronics Chemical Reviews 104 11 4891 4945 doi 10 1021 cr030666m PMID 15535637 Wudl F Kaplan M L 1979 2 2 Bi L 3 Dithiolylidene Tetrathiafulvalene TTF and its Radical Cation Salts Inorganic Syntheses Vol 19 pp 27 30 doi 10 1002 9780470132500 ch7 ISBN 978 0 470 13250 0 a href Template Cite book html title Template Cite book cite book a journal ignored help D Chasseau G Comberton J Gaultier C Hauw 1978 Reexamen de la structure du complexe hexamethylene tetrathiafulvalene tetracyanoquinodimethane Acta Crystallographica Section B 34 2 689 Bibcode 1978AcCrB 34 689C doi 10 1107 S0567740878003830 Wudl F Wobschall D Hufnagel E J 1972 Electrical Conductivity by the Bis 1 3 dithiole bis 1 3 dithiolium System J Am Chem Soc 94 2 670 672 doi 10 1021 ja00757a079 Ferraris J Cowan D O Walatka V V Jr Perlstein J H 1973 Electron transfer in a new highly conducting donor acceptor complex J Am Chem Soc 95 3 948 949 doi 10 1021 ja00784a066 Larsen J Lenoir C 1998 2 2 Bi 5 6 Dihydro 1 3 Dithiolo 4 5 b 1 4 dithiinylidene BEDT TTF Organic Syntheses a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Collected Volumes vol 9 p 72 Further reading editRovira C 2004 Bis ethylenethio tetrathiafulvalene BET TTF and Related Dissymmetrical Electron Donors From the Molecule to Functional Molecular Materials and Devices OFETs Chemical Reviews 104 11 5289 5317 doi 10 1021 cr030663 PMID 15535651 Iyoda M Hasegawa M Miyake Y 2004 Bi TTF Bis TTF and Related TTF Oligomers Chemical Reviews 104 11 5085 5113 doi 10 1021 cr030651o PMID 15535643 Frere P Skabara P J 2005 Salts of Extended Tetrathiafulvalene analogues relationships Between Molecular Structure Electrochemical Properties and Solid State Organization Chemical Society Reviews 34 1 69 98 doi 10 1039 b316392j PMID 15643491 Gorgues Alain Hudhomme Pietrick Salle Marc 2004 Highly Functionalized Tetrathiafulvalenes Riding along the Synthetic Trail from Electrophilic Alkynes Chemical Reviews 104 11 5151 5184 doi 10 1021 cr0306485 PMID 15535646 Physical properties of Tetrathiafulvalene from the literature Segura Jose L Martin Nazario 2001 New Concepts in Tetrathiafulvalene Chemistry Angewandte Chemie International Edition 40 8 1372 1409 doi 10 1002 1521 3773 20010417 40 8 lt 1372 aid anie1372 gt 3 0 co 2 i PMID 11317287 Retrieved from https en wikipedia org w index php title Tetrathiafulvalene amp oldid 1215918132, wikipedia, wiki, book, books, library,
