- Synthesis and nanostructures of several tetrathiafulvalene derivatives having the side chains composed of chiral and hydrogen-bonding groups and their charge-transfer complexes
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Tetrathiafulvalene (TTF) derivatives TTF-Bor, TTF-2UM and TTF-4UM having chiral urethane groups were prepared. Among them, TTF-2UM, TTF-4UM and their charge-transfer (CT) complexes with F4TCNQ organized the nanowires. The intermolecular hydrogen bonding of the chiral urethane groups and π-stacking of TTF moieties or the formation of CT complexes resulted in a long one-dimensional nanowires. The chiral moieties were responsible for the molecular orientation of TTF cores to give helical structures. Electronic conductivity of the films of nanowires composed of TTF-2UM and TTF-4UM with F4TCNQ were determined to be 8.0 × 10-2 and 3.2 × 10-2 S cm-1, respectively.
- Tatewaki, Yoko,Watanabe, Takanori,Watanabe, Koji,Kikuchi, Kohei,Okada, Shuji
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- Fabrication and operation of monolayer mott FET at room temperature
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Self-assembled monolayer FET based on a TTF derivative is described (FET = field-effect-transistor, TTF = tetrathiafulvalene). The molecule is anchored on an alumina dielectric layer through covalent bonding of a phosphonic acid linker. A p-type monolayer FET device is achieved and subsequent chemical doping of this monolayer with F4TCNQ dopants results in an ambipolar device. (F4TCNQ = 2,3,5,6-Tetrafluoro- 7,7,8,8-tetracyanoquinodimethane) Several strange behaviors including a gate voltage shift upon doping seem to be consistent with organic monolayer Mott FET. Finally, temperature dependence of the FET performance, which also fit the anticipated Mott FET behavior, is discussed.
- Yang, Fan,Suda, Masayuki,Yamamoto, Hiroshi M.
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- The chemistry of TTFTT; 1: New efficient synthesis and reactions of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFTT): An important building block in TTF-syntheses
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An improved and efficient synthesis of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFTT) 5 is reported. TTF-tetrathiolate 5 was generated from 2,3,6,7-tetrakis(2'-cyanoethylthio)tetrathiafulvalene (11) under basic conditions at room temperature and was subsequently reacted with a range of electrophiles giving improved synthesis of known systems as well as new TTF-derivatives in excellent yields.
- Svenstrup,Rasmussen,Hansen,Becher
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- Bis(trisubstituted tetrathiafulvalenyl) disulfides: Disulfide-bridged TTF dimers
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The title compounds are synthesized, using the oxidative coupling of TTF thiolates. The disulfide linkage induces approximate orthogonality between the two TTF units, while maintaining virtually unchanged their electrochemical properties.
- Leriche, Philippe,Giffard, Michel,Riou, Amedee,Majani, Jean-Philippe,Cousseau, Jack,Jubault, Michel,Gorgues, Alain,Becher, Jan
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- New tetrathiafulvalenes containing carbazole and 1,3,5-triazine fragments: Synthesis, electro-chemical and optical properties
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New tetrathiafulvalenes, containing carbazole and 1,3,5-triazine fragments added to the tetrathia-fulvalene ring by means of a S-CH2-CH 2-O bridge, were synthesized. The electrochemical properties of the initial compounds and of the final products were investigated by cyclic voltammetry. The optical characteristics of their solutions were studied by UV absorption spectroscopy and fluorescence spectroscopy.
- Ignatenko,Gorbunov,Shklyaeva,Abashev
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- Chiral EDT-TTF precursors with one stereogenic centre: Substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
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Modulation of the packing of the donors in the solid state and of the conducting behaviour is achieved in chiral radical cation salts based on the mono-alkylated donors methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF 1) and ethyl-ethylenedithio-tetrathiafulvalene (Et-EDT-TTF 2), underlining the paramount role of the number of stereogenic centres and substituent steric hindrance. Both donors have been prepared as racemates and then separated as pure enantiomers by chiral HPLC. Electrocrystallization experiments provided two complete series of crystalline radical cation salts formulated as [(R)-1]2PF6, [(S)-1]2PF6, and [(rac)-1]2PF6 and [(R)-2]2PF6, [(S)-2]2PF6 and [(rac)-2]PF6·(THF), respectively. The mixed valence salts of 1 show metal-like conductivity in the high temperature regime, while the radical cation salts of 2 are semiconductors, with a much higher conductivity for the enantiopure compounds than the racemic one. Tight-binding band structure calculations of the extended Hückel type performed for all the materials explain the observed conducting behaviour and show the differences in the intermolecular interactions triggered by the change of substituent between 1 and 2.
- Mroweh, Nabil,Auban-Senzier, Pascale,Vanthuyne, Nicolas,Canadell, Enric,Avarvari, Narcis
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- Donor/acceptor interactions in self-assembled monolayers and their consequences on interfacial electron transfer
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The supramolecular association of tetrathiafulvalene (TTF) donors and bipyridinium acceptors is employed routinely to direct the formation of host/guest complexes and interlocked molecules in bulk solution. We have reproduced these donor/acceptor interactions at electrode/solution interfaces and demonstrated their pronounced influence on heterogeneous electron transfer. Specifically, we have synthesized a TTF with an oligomethylene arm terminated by a thiol group and assembled monolayers of this compound on gold. We have observed that the cyclic voltammogram of the immobilized TTF donors varies significantly upon addition of benzyl viologen, tetracyanoquinodimethane (TCNQ), or tetracyanoethylene (TCNE) acceptors to the electrolyte solution. Indeed, the supramolecular association of the complementary donors and acceptors results in a pronounced current decrease for the TTF redox waves. Consistently, the electrochemical response of the acceptors changes dramatically in the presence of TTF donors on the electrode surface. Instead, hexadecanethiolate monolayers, lacking the TTF donors at the termini of the oligomethylene chains, have a marginal influence on the voltammograms of the acceptors. Impedance measurements indicate that the charge-transfer resistance (RCT) for the reduction of the acceptors increases from less than 0.3 k?, at bare gold, to 324, 24, and 43 k? for benzyl viologen, TCNQ, and TCNE, respectively, at TTF-coated electrodes. By contrast, the electrode coating has a negligible influence on the cyclic voltammogram and impedance response of ferrocene, which cannot sustain donor/acceptor interactions with the immobilized TTFs. Thus, our results demonstrate that the interfacial complexation of complementary donors and acceptors has a dramatic effect on the heterogeneous electron transfer to and from the associated components.
- Pacsial, Eden J.,Alexander, Daniel,Alvarado, Robert J.,Tomasulo, Massimiliano,Raymo, Francì§isco M.
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- New π-extended donors: Synthesis, characterization, electrochemical and electrical conductivity studies
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A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of the
- Zitouni, Amel,Gouasmia, Abdelkrim,Bouguessa, Sabrina,Kaboub, Lakhemici,Boudiba, Louiza
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- Luminescence switching of a cyclometalated iridium(III) complex through a redox-active tetrathiafulvalene-based ligand
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A tetrathiafulvalene (TTF) moiety through an acetyl acetonate bridge to a phosphorescent Iridium (Ir) core with a luminescent active MLCT excited state to observe redox controlled electronic coupling between the inorganic metal luminophore and TTF spacer through distinct luminescent behaviours has been reported. The TTF structure was confirmed by mass spectrometry and NMR spectrocopy. The phosphorescence property of complexes can be modulated by ET-acac ligand, which exhibits different photo-induced electron transfer efficiencies of TTF in distinct oxidation states. The target compound may serve as a novel model compound to investigate the mechanism of charge transfer between Ir based luminescent layer and conductive layer, such as derivative, in OLED materials. The singlet-triplet interactions at excited states contribute to the dynamic π-d coupling in TTF-based metal compounds.
- Xu, Chun-Hu,Sun, Wei,Zhang, Chao,Zhou, Can,Fang, Chen-Jie,Yan, Chun-Hua
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- New tetrathiafulvalenes containing a 2,5-bis(thiophen-2-yl)pyrrole fragment: Synthesis, optical properties, and electrochemical behavior
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The reaction of 1-(3-bromopropyl)-2,5-bis(thiophen-2-yl)-1H-pyrrole with cesium 5-methylsulfanyl-2-thioxo-1,3-dithiole-4-thiolate generated in situ gave previously unknown 4-{3-[2,5-bis(thiophen-2-yl)-1H-pyrrol-1-yl]propylsulfanyl}- 5-methylsulfanyl-1,3-dithiole-2-thione, and cross-coupling of the latter with 4,5-disubstituted 1,3-dithiole-2-thiones in the presence of triethyl phosphite afforded new substituted tetrathiafulvalenes containing a 2,5-bis(thiophen-2-yl) pyrrole fragment. Optical properties and electrochemical behavior of the synthesized compounds were studied, and their ability to undergo electropolymerization was confirmed.
- Ignatenko,Shklyaeva,Abashev
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- Dithiolene dimetallic molybdenum(v) complexes displaying intraligand charge transfer (ILCT) emission
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Bifunctional dithiolene ligands have been coordinated to the Mo V(O)(μ-S2)MoV(O) unit to afford [Mo 2O2(μ-S)2(BPyDTS2) 2]2- (12-) (BPyDTS2 (2-bis-(2-pyridyl)methylene-1,3-dithiolene) dianions. Reaction of the 1 2- molybdenum dimer with pentacarbonylchlorothenium(i) affords a tetrametallic complex of formula [Mo2O2(μ-S) 2(BPyDTS2)2{Re(CO)3Cl} 2]2- (22-). The monomeric (CH3) 2Sn(BPyDTS2) (3) tin complex has also been prepared for comparative purposes. In the structure of (Et4N)2[1], the two metal atoms are in a square pyramidal coordination environment defined by two bridging sulfur atoms, one terminal oxygen atom and the two sulfur atoms of the bifunctional dithiolene ligand. This arrangement leaves two nitrogen atoms on each side which coordinate to two Re atoms in the 22- tetrametallic complex. Compound 3 has a distorted tetrahedral structure defined by two carbon atoms of the methyl groups and two sulfur atoms of the dithiolene ligand. The luminescence properties of all three complexes in acetonitrile have been investigated. Detailed studies supported on quantum mechanical calculations revealed that complex 12- shows photoluminescence in the 600-800 nm region with a maximum wavelength of 628 nm and an emission quantum yield of 0.092, associated with an intraligand charge transfer (ILCT) transition. Coordination of two Re(CO)3Cl fragments to 12- to afford 22- does not affect the emission spectrum and shape although it decreases the quantum yield, approximately by a factor of 4.6. Compound 3 exhibits a similar emission spectrum to those of the complexes 12- and 22- in good agreement with the ILCT assignment. The quantum yield of 3 lies between that of the 12- and 22- complexes.
- Recatala, David,Gushchin, Artem L.,Llusar, Rosa,Galindo,Brylev, Konstantin A.,Ryzhikov, Maxim R.,Kitamura, Noboru
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- Preparation and characterization of metal complexes with an extended TTF dithiolato ligand, bis(propylenedithiotetrathiafulvalenedithiolato)-nickelate and -cuprate
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Novel monoanionic nickel and dianionic copper complexes with the extended TTF dithiolato ligand, propylenedithiotetrathiafulvalenedithiolate [ptdt2- =(S8C9H6)2-], have been synthesized. Characterization of monoanionic tetraphenylphosphonium and tetramethylammonium salts of Ni(ptdt)2- and the dianionic tetraphenylphosphonium salt of Cu(ptdt)22- have been performed, using cyclic voltammetry, electrical resistivity measurements, magnetic susceptibility measurements and X-ray crystal structure determination. The geometries around the Ni atoms are almost square planar. In both Ni complexes, one of the extended ligands of Ni(ptdt)2- is overlapping with that of the adjacent anion separated by about half of the unit of the molecule, forming a one-dimensional chain. The adjacent chains are connected by transverse short S...S contacts. Cu(ptdt)22- has a distorted tetrahedral geometry around the Cu atom and the dihedral angle between the planes of the dithiolato ligand is 54.2°. The crystal structures of Ni(ptdt)2- and Cu(ptdt)22- complexes show the possibility of novel 2D or 3D intermolecular contacts through ptdt ligands. The complex [Me4N][Ni(ptdt)2]·Me2CO is a semiconductor with a room temperature conductivity of 1.4 × 10-3 S cm-1 and activation energy of 9.9 × 10-2 eV.
- Kumasaki, Mieko,Tanaka, Hisashi,Kobayashi, Akiko
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- Synthesis and characterization of a tetrathiafulvalene-based polymer
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A novel tetrathiafulvalene (TTF)-based main-chain polymer (6TTF-polymer) was successfully synthesized via a condensation polymerization between a newly synthesized dihydroxy TTF derivative and a malonyl chloride, and its chemical structure was characteriz
- Lee, Sehyun,Wang, Lei,Hwang, Seok-Ho,Lee, Myong-Hoon,Jeong, Kwang-Un
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scheme or table
p. 1451 - 1456
(2012/07/14)
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- Synthesis, spectroscopic, and electrochemical properties of three tetrathiafulvalenes attached to perylene
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Three donor-acceptor dyads 1-3 comprising of a tetrathiafulvalene (TTF) unit linked with perylene by a simple σ-bond were synthesized and characterized. Spectroscopy and cyclic voltammetry provided an indication that intramolecular charge-transfer interactions in their ground states between TTF and perylene for dyads 1-3 are negligible. Compared with the compound perylene, dyads 1-3 exhibited large fluorescence quenching, which might be ascribed to photo-induced electron transfer interaction between TTF and perylene units in the excited state.
- Qiu, Haixiao,Wang, Chengyun,Xu, Jinfeng,Lai, Guoqiao,Shen, Yongjia
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scheme or table
p. 1357 - 1362
(2009/12/05)
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- Synthesis, structure and electrochemical properties of two new unsymmetrical tetrathiafulvalene derivatives
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Two new unsymmetrical tetrathiafulvalene (TTF) derivatives, 2,3-bis(cyanoethylthio)-6,7-(methylethylenedithio)tetrathiafulvalene (6a) and 2,3-bis(cyanoethylthio)-6,7-(cyclopentodithio)tetrathiafulvalene (6b), have been prepared and characterized by NMR, MS, IR and Elemental analyses. The molecular structures have been determined by X-ray crystallography. Their redox properties have been investigated by cyclic voltammetry in dichloromethane solution and each compound shows two reversible single-electron redox couples.
- Xu, Ming,Ji, Yong,Zuo, Jing-Lin,Li, Yi-Zhi,You, Xiao-Zeng
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p. 847 - 850
(2007/10/03)
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- Facile syntheses of 4-(2-cyanoethylthio)-1,3-dithiole-2-thione and new electron donors with two TTF units and compounds with bis(1,3-dithiole-2-thione) groups
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The synthetic conditions for the preparation of 4-(2-cyanoethylthio)-1,3-dithiole-2-thione (1) from TBA2?[Zn(dmit)2] were studied. Compound 1 was used to synthesize new electron donors with two tetrathiafulvalene (TTF) units. Other i
- Jia, Chunyang,Zhang, Deqing,Guo, Xuefeng,Wan, Shuhui,Xu, Wei,Zhu, Daoben
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p. 2177 - 2182
(2007/10/03)
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- A new approach to 4-alkylthio-1,3-dithiole-2-thione: An unusual reaction of a zinc complex of 1,3-dithole-2-thione-4,5-dithiolate
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(formula presented) A new and facille approach to 4-alkylthio-1,3-dithiole-2-thione starting from easily accessible reactants was described. This approach was based on the unusual reaction of a zinc complex of 1,3-dithiole-2-thione-4,5-dithiolate with electrophilic reagents in the presence of 3-picolyl chloride hydrochloride/or 4-picolyl chloride hydrochloride/or pyridine hydrochloride.
- Jia, Chunyang,Zhang, Deqing,Xu, Wei,Zhu, Daoben
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p. 1941 - 1943
(2007/10/03)
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- Sequential functionalisation of bis-protected tetrathiafulvalene-dithiolates
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The utilisation of the 2-cyanoethyl group as a versatile protecting group for 2-thioxo-1,3-dithiole-4,5-dithiolates and tetrathiafulvalene-thiolates is reported. Mono deprotection of bis-protected 2-thioxo-1,3-dithiole-4,5-dithiolate and of bis-protected
- Simonsen, Klaus B.,Svenstrup, Niels,Lau, Jesper,Simonsen, Ole,Mork, Pernille,Kristensen, Gitte J.,Becher, Jan
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p. 407 - 418
(2007/10/03)
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- Synthesis of New 2H-1,3-Dithiol-2-thiones and -2H-1,3-Dithiol-Ones, the Intermediates for Tetrathiafulvalenes and Metal Dithiolates
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The synthesis of 2H-1,3-dithiol-2-thiones substituted in positions 4 and 5 was performed by the ring cleavage in 2,5,7,9-tetrathiobicyclonon-1(6)en-3-on-8-thione by sodium methoxide followed by alkylation of the obtained thiolate.The reactions of 2,4,5-tetrahydro-1,3-dithiol-2,4,5-trithione with cyclopentadiene, indene, diethylvinyldithiocarbamate, and allyl bromide, resulting new, earlier unaccessible, 2H-1,3-dithiol-2-thiones were carried out.Synthesis of new 2H-1,3-dithiol-3-thiones with substituents in 4 and 5 positions is performed; some of these compounds were transformed into related diketones by reacting with mercury acetate.New tetrathiofulvalenes are obtained.
- Abashev, G. G.,Russkikh, V. S.,Shklyaeva, E. V.,Vladykin, V. I.
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p. 1533 - 1537
(2007/10/03)
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