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Search for "TTF" in Full Text gives 43 result(s) in Beilstein Journal of Organic Chemistry.

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

  • Yoann Cotelle,
  • Marie Hardouin-Lerouge,
  • Stéphanie Legoupy,
  • Olivier Alévêque,
  • Eric Levillain and
  • Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

Graphical Abstract
  • tetrathiafulvalene (TTF) sidewalls have been synthesized through different strategies with the aim of investigating the effect of electrochemical and spatial properties for binding neutral accepting guests. We have in particular focused our study on the spacer extension in order to tune the intramolecular TTF···TTF
  • distance within the clip and, consequently, the redox behavior of the receptor. Carried out at different concentrations in solution, electrochemical and spectroelectrochemical experiments provide evidence of mixed-valence and/or π-dimer intermolecular interactions between TTF units from two closed clips
  • . The stepwise oxidation of each molecular clip involves an electrochemical mechanism with three one-electron processes and two charge-coupled chemical reactions, a scheme which is supported by electrochemical simulations. The fine-tunable π-donating ability of the TTF units and the cavity size allow to
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Published 17 Jun 2015

Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

  • Masashi Hasegawa,
  • Junta Endo,
  • Seiya Iwata,
  • Toshiaki Shimasaki and
  • Yasuhiro Mazaki

Beilstein J. Org. Chem. 2015, 11, 972–979, doi:10.3762/bjoc.11.109

Graphical Abstract
  • carried out by direct C–H activation of the TTF unit, and the chiroptical properties of the resulting polymer were also investigated. Keywords: allene; axial chirality; chiroptical properties; redox; tetrathiafulvalene; Introduction Recently, there has been a growing interest in chiral π-conjugated
  • switchable by tuning the electronic structure of the tetrathiafulvalene (TTF) moieties. However, compound 1 exhibited slow racemization in solution under daylight. The chirality of an allene is configurationally firm in general, because the barrier of the rotation of the allenic double bonds is quite high
  • latter of which is a dissymmetric allene having a TTF and a pyrenyl group at 1,3-position, suggests that the direct connection of the TTF units may strongly affect the fast racemization [14]. From this point of view, we decided to employ a 1,3-diphenylallene derivative (3) as a stable chiral framework
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Published 08 Jun 2015

Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

  • Sébastien Bivaud,
  • Sébastien Goeb,
  • Vincent Croué,
  • Magali Allain,
  • Flavia Pop and
  • Marc Sallé

Beilstein J. Org. Chem. 2015, 11, 966–971, doi:10.3762/bjoc.11.108

Graphical Abstract
  • obtain, from one given ligand, one single and stable assembly whose cavity size can be controlled. We recently depicted the preparation and properties of redox-active rings [29][35] and cages [36][37][38][39][40] integrating the tetrathiafulvalene (TTF) skeleton. In particular, we described self
  • -assembled containers prepared from an electron-rich ligand precursor based on the extended-TTF framework (exTTF) [39]. On this basis, we report herein that the size and the shape of coordination-driven self-assembled redox-active cages, constructed from a exTTF-based tetratopic ligand, can be tuned by
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Published 05 Jun 2015

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

  • Yunfei Wang and
  • Yuming Zhao

Beilstein J. Org. Chem. 2015, 11, 957–965, doi:10.3762/bjoc.11.107

Graphical Abstract
  • analysis, showing a BET surface of 148.2 m2 g−1 and an average pore diameter of 10.2 nm. Keywords: complexation; coordination polymers; porosity; redox activity; tetrathiafulvalene; Introduction Tetrathiafulvalene (TTF) has been widely applied as a redox-active building block in organic electronic
  • materials and supramolecular assemblies [1][2][3][4][5], since the first discovery by Wudl and others in the early 1970s that TTF upon interactions with suitable electron acceptors could give rise to charge-transfer complexes exhibiting excellent metallic conductivity [6][7]. The remarkable electron
  • -donating properties of TTF arise from its aromaticity-stabilized cationic states after releasing one and/or two electrons [1][2][3][4][5][8][9][10]. Tetrathiafulvalene vinylogues (TTFVs) are π-extended analogues of TTF bearing extended vinyl bridges between the two dithiole rings of TTF [9][10][11
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Published 03 Jun 2015

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

  • Sandrina Oliveira,
  • Dulce Belo,
  • Isabel C. Santos,
  • Sandra Rabaça and
  • Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

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  • Sandrina Oliveira Dulce Belo Isabel C. Santos Sandra Rabaca Manuel Almeida C²TN, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, P-2695-066 Bobadela LRS, Portugal 10.3762/bjoc.11.106 Abstract A dissymmetric TTF-type electron donor, cyanobenzene-ethylenedithio
  • -tetrathiafulvalene (CNB-EDT-TTF), was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic
  • voltammetry, NMR, UV-visible and IR spectroscopy. Keywords: cross-coupling; cyanobenzene; cyclic voltammetry; dissymmetric tetrathiafulvalene; electro-active donors; Introduction The tetrathiafulvalene molecule (TTF) and its many derivatives, due to its unique π-donor properties, have been at the basis of
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Published 03 Jun 2015

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

  • Huixin Jiang,
  • Virginia Mazzanti,
  • Christian R. Parker,
  • Søren Lindbæk Broman,
  • Jens Heide Wallberg,
  • Karol Lušpai,
  • Adam Brincko,
  • Henrik G. Kjaergaard,
  • Anders Kadziola,
  • Peter Rapta,
  • Ole Hammerich and
  • Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2015, 11, 930–948, doi:10.3762/bjoc.11.104

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  • /bjoc.11.104 Abstract A selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF) units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and
  • tetraethynylethene (trans-substituted) units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic arrangements. The cyclic structures correspond to so-called radiaannulenes having both endo- and exocyclic double bonds. Interactions between two redox-active TTF units in these molecules
  • ; tetraethynylethene; tetrathiafulvalene; Introduction Linking together two redox-active tetrathiafulvalene (TTF) units by a π-conjugated bridge has found immense interest in materials science, in particular in the quest for organic conductors [1][2][3]. Thus, the materials properties rely on the degree of intra- and
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Published 02 Jun 2015

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

  • Vladimir A. Azov,
  • Diana Janott,
  • Dirk Schlüter and
  • Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

Graphical Abstract
  • processes in molecular and supramolecular systems [3][4]. Availability of selective synthetic methods [5][6] gave access to differently substituted tetrathiafulvalene (TTF) moieties which allowed tuning of oxidation potential, donating ability, as well as other physical and chemical properties. The
  • regioselective functionalization of TTF, however, remains problematic due to the presence of four identical attachment sites. Incorporation of the TTF moiety in macrocycles usually leads to poorly separable mixtures of cis/trans isomers [7][8][9]. Even if separation is possible, TTFs are prone to cis/trans
  • isomerization, which can be induced by light [10] or traces of acid [11]. These problems are aggravated by the fact that each reversible oxidation–reduction cycle of the TTF moiety always leads to formation of cis/trans isomer mixtures. Bis-pyrrolotetrathiafulvalenes 2 and monopyrrolotetrathiafulvalenes (MPTTFs
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Published 21 May 2015

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties

  • Longfei Ma,
  • Jibin Sun,
  • Xiaofeng Lu,
  • Shangxi Zhang,
  • Hui Qi,
  • Lei Liu,
  • Yongliang Shao and
  • Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 850–859, doi:10.3762/bjoc.11.95

Graphical Abstract
  • –, and coexistence of planar [Cu(II)Br4]2– and tetrahedral [Cu(II)Br3]– ions. On the other hand, the TTFs show either radical cation or dication states that depend on their redox potentials. The central TTF framework on most of TTFs is nearly planar despite the charge on them, whereas the two dithiole
  • : antiferromagnetic interaction; arylthio-substituted tetrathiafulvalenes; charge-transfer; crystal structure; magnetic property; Introduction Since firstly synthesized in 1970s [1], tetrathiafulvalene (TTF) and its derivatives have been intensively studied to explore functional organic materials [2]. Inspired by
  • the discovery of highly conducting charge-transfer (CT) complex TTF·TCNQ [3] and the first organic superconductor (TMTSF)2X [4], the chemical modifications on TTF are traditionally aimed at the creation of organic conductors with various electronic ground states [5][6][7][8][9][10]. It has been well
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Published 20 May 2015

Trifluoromethyl-substituted tetrathiafulvalenes

  • Olivier Jeannin,
  • Frédéric Barrière and
  • Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

Graphical Abstract
  • -withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations
  • . Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the σmeta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that
  • these observations and also show that the low energy HOMO–LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO→LUMO + 1 transition. Despite relatively high oxidation
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Published 06 May 2015

TTFs nonsymmetrically fused with alkylthiophenic moieties

  • Rafaela A. L. Silva,
  • Bruno J. C. Vieira,
  • Marta M. Andrade,
  • Isabel C. Santos,
  • Sandra Rabaça,
  • Dulce Belo and
  • Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

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  • , Portugal 10.3762/bjoc.11.71 Abstract Two new dithiolene ligand precursors, containing fused TTF and alkyl thiophenic moieties 3,3'-{[2-(5-(tert-butyl)thieno[2,3-d][1,3]dithiol-2-ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-tbtdt, 1), and 3,3'-{[2-(5-methylthieno[2,3-d][1,3]dithiol-2
  • /AgCl, typical of TTF donors at E11/2 = 279 V and E21/2 = 680 V for 1 and E11/2 = 304 V and E21/2 = 716 V in the case of 2. The single-crystal X-ray structure of 1 and of a charge transfer salt of 2, (α-mtdt)[Au(mnt)2] (3), are reported. Keywords: cyclic voltammetry; single-crystal X-ray diffraction
  • ; supramolecular chemistry; tetrathiafulvalene (TTF); thiophene; Introduction Since the discovery of the first organic metals and superconductors the field of electronic molecular materials has been largely dominated by derivatives of the organic donor tetrathiafulvalene (TTF) [1]. More than one thousand TTF
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Published 05 May 2015

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

  • Erdal Ertas,
  • İlknur Demirtas and
  • Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

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  • Gebze-Kocaeli, Turkey 10.3762/bjoc.11.46 Abstract This review aims to give an overview of the current status of our research on the synthesis of π-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, ET) analogues prepared from 1,8-diketones via a ring forming reaction. The new synthesized π
  • -electron donors have vinyl moieties producing extended π-electron delocalization over the substituent phenyl rings at the peripheries. Keywords: bis(ethylenedithio)tetrathiafulvalene; bis(vinylenedithio)tetrathiafulvalene; tetrathiafulvalene; Introduction Tetrathiafulvalene (TTF, 1, Figure 1) was first
  • with the discovery of the salt of 1 with 7,7,8,8-tetracyanoquinodimethane (2, TTF-TCNQ) in 1973 [4]. Since then, studies have been focused on the syntheses of donor TTF analogues and investigations of the physical properties of their charge-transfer (CT) salts with various acceptors for applications
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Published 27 Mar 2015

Redox active dendronized polystyrenes equipped with peripheral triarylamines

  • Toshiki Nokami,
  • Naoki Musya,
  • Tatsuya Morofuji,
  • Keiji Takeda,
  • Masahiro Takumi,
  • Akihiro Shimizu and
  • Jun-ichi Yoshida

Beilstein J. Org. Chem. 2014, 10, 3097–3103, doi:10.3762/bjoc.10.326

Graphical Abstract
  • tetrathiafulvalene (TTF) derivatives [15][16][17][18][19], the corresponding dendronized polymers are rare [20]. One of the major reasons for this seems to be the difficulty in making such structures. However, redox-active dendronized polymers should provide more opportunities to form functional organic materials
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Published 22 Dec 2014

Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C60

  • Marco Caricato,
  • Silvia Díez González,
  • Idoia Arandia Ariño and
  • Dario Pasini

Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132

Graphical Abstract
  • , have been reported and characterized in terms of thermodynamic stability by using fluorescence measurements [23]. Martin, Perez et al. have reported on a series of extended TTF units able to form strong complexes with C60 and C70 in organic solutions [24][25]. We have recently reported an efficient
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Published 06 Jun 2014

Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

  • Jiří Kulhánek and
  • Filip Bureš

Beilstein J. Org. Chem. 2012, 8, 25–49, doi:10.3762/bjoc.8.4

Graphical Abstract
  • ,abs = 324–367 nm and λmax,em = 393–470 nm, respectively [70]. In 2007, Liu et al. reported a very nice example of D-π-A system 63 based on benzimidazole as a parent π-conjugated backbone fused with TCAQ (tetracyanoanthraquinodimethane) and TTF (tetrathiafulvalene) as acceptor and donor moieties
  • systems 35–43 [25][62][63][64][65][66]. Structure of benzimidazoles (44–47), imidazophenanthrolines (48–57), imidazophenanthrenes (58–60), fluorophores 61, 62, and TCAQ-imidazo-TTF (63) chromophores [23][24][67][68][69][70][71]. General structures of bis(benzimidazole) chromophores 67–71 and pyridinium
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Published 05 Jan 2012

Redox-active tetrathiafulvalene and dithiolene compounds derived from allylic 1,4-diol rearrangement products of disubstituted 1,3-dithiole derivatives

  • Filipe Vilela,
  • Peter J. Skabara,
  • Christopher R. Mason,
  • Thomas D. J. Westgate,
  • Asun Luquin,
  • Simon J. Coles and
  • Michael B. Hursthouse

Beilstein J. Org. Chem. 2010, 6, 1002–1014, doi:10.3762/bjoc.6.113

Graphical Abstract
  • series of compounds by exploiting the unusual 1,4-aryl shift observed for electron-rich 1,3-dithiole-2-thione and tetrathiafulvalene (TTF) derivatives in the presence of perchloric acid. The mechanistic features of this rearrangement are discussed since this synthetic strategy provides an alternative
  • route for the synthesis and functionalisation of sulfur rich compounds including redox active compounds of TTFs, and a Ni dithiolene. Keywords: aldehydes; metal-coordination; rearrangement; sulfur heterocycles; tetrathiafulvalene; Introduction The search for novel structures derived from TTF has led
  • to extensive investigations of the chemistry of 1,3-dithiole-2-thione (1, Figure 1) [1][2], since this heterocycle and its derivatives are frequently used as convenient precursors to TTF compounds through phosphite-mediated coupling [3]. Our efforts to prepare triaryl derivatives of compound 1 led to
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Published 21 Oct 2010

Structure and reactivity in neutral organic electron donors derived from 4-dimethylaminopyridine

  • Jean Garnier,
  • Alan R. Kennedy,
  • Leonard E. A. Berlouis,
  • Andrew T. Turner and
  • John A. Murphy

Beilstein J. Org. Chem. 2010, 6, No. 73, doi:10.3762/bjoc.6.73

Graphical Abstract
  • of considerable selectivity in their reductions of organic substrates, and evidence is steadily accumulating to support this. Tetrathiafulvalene (TTF, 1, E11/2 = 0.37 V; E21/2 = 0.67 V in DCM vs SCE) [1], one of the weakest of these donors, reduces arenediazonium salts to aryl radicals [2][3][4][5][6
  • two electrons, as well as the stabilization of both the positive charge and radicals by the lone pairs on the sulfur atoms. The effect of aromatic stabilization is enhanced in the extended analogue 4; however, unlike TTF, this compound affords only an irreversible oxidation Ep = −0.14 V in MeCN
  • both the positive charge and an unpaired electron upon oxidation; this stabilization is greater than is afforded by sulfur in TTF. Benzimidazole-derived donor 6 (E11/2 = −0.82 V; E21/2 = −0.76 V vs SCE in DMF) [18][19][20], combines the stabilization of positive charge and of an unpaired electron
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Published 05 Jul 2010

Synthesis and redox behavior of new ferrocene- π-extended- dithiafulvalenes: An approach for anticipated organic conductors

  • Abdelwareth A. O. Sarhan,
  • Omar F. Mohammed and
  • Taeko Izumi

Beilstein J. Org. Chem. 2009, 5, No. 6, doi:10.3762/bjoc.5.6

Graphical Abstract
  • characterized a donor-acceptor dyad system involving tetrathiafulvalene (TTF) as electron donor attached by a flexible spacer to perylene derivatives as electron acceptor [5]. They have shown that the fluorescence of the tetrathiafulvalene–perylene derived dyad can be reversibly modulated by the transformation
  • of the TTF unit into its radical cation and dication. After organic chemists had discovered organic metal tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) charge transfer complexes, various synthetic approaches to tetrathiafulvalenes gained wide attention, and charge-transfer from TTF to TCNQ
  • was extensively recognized [6][7]. For instance, π-extended-dithiafulvalenes have been successfully used as multi-electron donor moieties with high electrical conductivities in the preparation of new charge transfer (CT) complexes [8][9]. However, a number of modifications of the TTF framework have
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Published 19 Feb 2009

Reduction of arenediazonium salts by tetrakis(dimethylamino)ethylene (TDAE): Efficient formation of products derived from aryl radicals

  • Mohan Mahesh,
  • John A. Murphy,
  • Franck LeStrat and
  • Hans Peter Wessel

Beilstein J. Org. Chem. 2009, 5, No. 1, doi:10.3762/bjoc.5.1

Graphical Abstract
  • , employing tetrathiafulvalene (TTF, 4a, Scheme 1) as electron donor. A number of functionalised heterocycles [5][6][7][8][9][10][11][12][13][14][15][16][17] such as dihydrobenzofurans, indolines and indoles have been synthesized using this methodology and the radical-polar methodology has been employed
  • formation of aryl radicals had never been reported using TDAE meant that we were keen to compare its reactions with those of the structurally related TTF (4a). Thus, as shown in Scheme 2, the radical-cation of TTF intercepts intermediates with the formation of C-S bonds in the radical-polar crossover
  • was consistent with reduction of the aryl radical to aryl anion and derived a value for the standard potential of this step as E0 = +0.05 V. The reduction potentials determined by Andrieux and Pinson would be consistent with the chemistry that we had observed using TTF, in that TTF had been able to
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Published 12 Jan 2009
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