68128-94-9Relevant articles and documents
Syntheses and Properties of Novel Dimeric Tetrathiafulvalenes Linked with an Ethenylene or Ethynylene Spacer
Otsubo, Tetsuo,Kochi, Yasutaka,Bitoh, Atsushi,Ogura, Fumio
, p. 2047 - 2050 (1994)
Conjugated dimeric TTFs linked with an ethenylene or ethynylene spacer were prepared as novel electron donors and preferentially formed 1:1 complexes with TCNQF4 and with DDQ, which were more conductive than those of monomeric TTFs.
Tetrathiafulvalene derivatives as NLO-phores: Synthesis, electrochemistry, Raman spectroscopy, theoretical calculations, and NLO properties of novel TTF-derived donor-π-acceptor dyads
Gonzalez,Segura,Seoane,Martin,Garin,Orduna,Alcala,Villacampa,Hernandez,Lopez Navarrete
, p. 8872 - 8882 (2001)
Novel π-conjugated donor-acceptor chromophores, based on the strong electron-donating tetrathiafulvalene moiety and different electron-withdrawing acceptors, exhibit large second-order optical nonlinearities. The effect of increasing the length of the polyenic spacer and the influence of the nature of the acceptor moiety on the NLO properties have been studied by using the electric field-induced second-harmonic generation (EFISH) technique as well as by semiempirical and ab initio theoretical calculations. A charge-transfer band has been observed in the absorption spectra of these D-π-A compounds that undergoes an hypsochromic shift when increasing the number of vinylenic spacer units connecting both donor and acceptor moieties. The degree of the intramolecular charge transfer from the donor to the acceptor has also been analyzed by means of Raman spectroscopy.
Iron(II) complexes based on π-conjugated terpyridine ligands with tetrathiafulvalene or its radical analogue
Hu, Liang,Liu, Wei,Li, Cheng-Hui,Zhou, Xin-Hui,Zuo, Jing-Lin
, p. 6037 - 6048 (2013)
Two tetrathiafulvalene (TTF) functionalized 2,2′:6′,2″- terpyridine derivatives, 4′-tetrathiafulvalene-2,2′:6′, 2″-terpyridine (L1) and 6,6″-dimethyl-4′- tetrathiafulvalene-2,2′:6′,2″-terpyridine (L2), were synthesized and characterized. Based on L1 and L2, four electrochemically active TTF-containing iron(II) complexes, [Fe II(L1)2][ClO4]2 (1), [FeII(L1·+)2][ClO4] 4 (2), [FeII(L1)2][CF 3SO3]2 (3) and [FeII(L 2)2][ClO4]2 (4), were successfully obtained. The preparation, spectroscopic and electrochemical properties of these new compounds as well as the crystal structures of complexes 1, 3 and 4 are described. Magnetic studies on 4 (with the ligand L2) suggest that the FeII ion is in the high-spin state. Complex 2 was isolated as an interesting and stable open-shell substance, and the free spin is mainly associated with the TTF radicals, as indicated by EPR, UV/Vis spectra, electrochemical analysis, spectroelectrochemical measurements and XPS spectra. After the oxidation and the formation of the radical cation, the electrical conductivity of 2 is almost 3 orders of magnitude higher than that of 1. DFT and TDDFT calculations provided insight into interpreting the electronic properties of complex 1 and its oxidized states. Four interesting iron(II) 4′-tetrathiafulvalene-2,2′:6′,2″-terpyridine (L 1) or 6,6″-dimethyl-4′-tetrathiafulvalene-2,2′: 6′,2″-terpyridine (L2) complexes and their spectroscopic, electrochemical and conductive properties are described. In the oxidized complex 2, the low-spin FeII ions are coordinated by two TTF radicals. XPS and DFT calculations were also conducted on some of the new compounds. Copyright
Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties
Souto, Manuel,Calbo, Joaquín,Ratera, Imma,Ortí, Enrique,Veciana, Jaume
, p. 11067 - 11075 (2017)
Three conjugated donor-π-acceptor radical systems (1 a–1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence
Selective Functionalization of Tetrathiafulvalene Using Mg- and Zn-TMP-Bases: Preparation of Mono-, Di-, Tri-, and Tetrasubstituted Derivatives
Nafe, Julia,Auras, Florian,Karaghiosoff, Konstantin,Bein, Thomas,Knochel, Paul
, p. 5356 - 5359 (2015)
The tetrathiafulvalene-scaffold (TTF) reacts selectively in allylation, acylation, arylation, halogenation, and thiolation reactions via magnesium or zinc derivatives that are obtained by a direct metalation with Mg- and Zn-TMP-bases (TMP = 2,2,6,6-tetram
Evidence for Two Separate One-Electron Transfer Events in Excited Fulleropyrrolidine Dyads Containing Tetrathiafulvalene (TTF)
Martin, Nazario,Sanchez, Luis,Angeles Herranz,Guldi, Dirk M.
, p. 4648 - 4657 (2000)
1,3-Dipolar cycloadditions of TTF-azomethine ylides (TTF = tetrathiafulvalene) to C60 have been used to synthesize a series of novel donor-bridge-acceptor dyads. In these dyads the pyrrolidine[3′,4′: 1,2][60]fullerene is covalently attached to the electron donor TTF either directly (5) or alternatively through one (2a) or two (7) vinyl groups. In the ground state, dyads 2a, 5, and 7 undergo four quasireversible one-electron reductions and two reversible oxidation steps. The former are associated with the reduction of the C60 core, whereas the latter correspond to the formation of the radical cation and dication of the TTF moiety, respectively. Semiempirical PM3 calculations reveal donor-acceptor distances of 4.8 A (5), 7.6 A (2a), and 10.5 A (7), and a deviation from planarity between the TTF fragment and the vinylogous spacer. In relation to an N-methylfulleropyrrolidine, the emission of the fullerene singlet excited state in dyads 2a, 5, and 7 is substantially reduced. Furthermore, the fluorescence quantum yield correlates well with the solvent dielectric constant and also with the spatial separation of the donor and acceptor moieties in the dyads. These correlation suggest that intramolecular electron-transfer processes evolving from the fullerene singlet excited state generate the (C60?-)-(TTF?+) pair. Pico- and nanosecond-resolved transient spectroscopy further substantiate a rapid transformation of the initially formed singlet excited state into the charge-separated radical pair with intramolecular rates ranging between 1.17 × 1010 s-1 and 1.47 × 109 s-1. In all cases, the product of back electron transfer is the triplet excited state, which is generated with markedly high quantum yields (0.61-0.97). The latter is, in addition to the rapid primary intramolecular electron transfer, subject to a slower, secondary intermolecular electron transfer with rate constants of 7 × 108 M-1s-1 (5) in benzonitrile and 1.6 × 109 M- s-1 (5) in toluene.
Electroactive supramolecular self-assembled fibers comprised of doped tetrathiafulvalene-based gelators
Kitamura, Tetsu,Nakaso, Suguru,Mizoshita, Norihiro,Tochigi, Yusuke,Shimomura, Takeshi,Moriyama, Masaya,Ito, Kohzo,Kato, Takashi
, p. 14769 - 14775 (2005)
New electroactive supramolecular fibers have been formed by self-assembly of the derivatives of tetrathiafulvalene (TTF) in liquid crystals. These derivatives are designed and prepared by introducing the TTF moiety to the scaffold derived from amino acids such as L-isoleucine whose derivatives function as organogelators. These TTF-based gelators form stable fibrous aggregates in liquid crystals. These fibers are the first example of hydrogen-bonded one-dimensional aggregates having electroactive moieties whose electrical conductivities were measured after doping. Their electronic states have also been characterized by spectroscopic methods. Unidirectionally aligned fibers are formed in the oriented liquid crystal solvents on the rubbed polyimide surface for further functionalization of the fibers.
Preparation and valence tautomeric behavior of a cobaltdioxolene complex with a new TTF-functionalized phenanthroline Ligand
Kanegawa, Shinji,Kang, Soonchul,Sato, Osamu
supporting information, p. 700 - 702 (2013/07/26)
In this study, a new tetrathiafulvalene-functionalized phenanthroline ligand (TTF-phen) and a mononuclear cobalt(II) complex with a redox active 3,6-di-tert-butylsemiquinonato (3,6-dtsq) ligand was synthesized. Magnetic measurementsand IR spectroscopy suggested that the Co complex [Co(3,6- dtsq)2(TTF-phen)] exhibited thermally induced valence tautomerismin the temperature range 130400 K. This complex is the first example of a valence tautomeric complex with a TTFfunctionalized ligand.
The parent tetrathiafulvalene-terpyridine dyad: Synthesis and metal binding properties
Belhadj, Esmah,El-Ghayoury, Abdelkrim,Mazari, Miloud,Sallé, Marc
, p. 3051 - 3054 (2013/06/27)
The still unknown parent tetrathiafulvalene-terpyridine- ligand 5 (namely TTF-terpy), was synthesized through a straightforward strategy. The dyad exhibits an intramolecular charge transfer (ICT) which was evidenced by UV-vis electronic absorption. Complexation of various transition metal cations by this redox-active ligand was studied by UV-vis absorption spectroscopy as well as by cyclic voltammetry titration studies, supporting the dual functional character of this system. In addition, these results demonstrate that ligand 5 is a suitable building block for the preparation of electroactive neutral as well as charged metal complexes.
Tetrathiafulvalene (TTF)-functionalized thiophene copolymerized with 3,3′-didodecylquaterthiophene: Synthesis, TTF trapping activity, and response to trinitrotoluene
Sinha, Jasmine,Lee, Stephen J.,Kong, Hoyoul,Swift, Thomas W.,Katz, Howard E.
, p. 708 - 717 (2013/04/24)
We report a synthesis route to a thiophene polymer where the repeat unit consists of 3,3′-didodecylquaterthiophene (as in PQT12) plus an additional thiophene ring from which other functional groups may be projected. The hydroxymethyl form of this polymer, while only a poor semiconductor in its own right, serves as a vehicle for compatibilizing PQT12 itself with arbitrary functional groups. In this article, we focus on tetrathiafulvalene (TTF) as the functionality. As expected, the TTF group acts as a hole trap, as shown by loss of hole mobility and a surprising negative Seebeck coefficient, but this enables a current-increase response to trinitrotoluene as an analyte and confirms a similar observation we recently reported for a dissolved TTF. Added dopants also fill the trap states, restoring hole mobility and the typical positive Seebeck coefficient.
