Synthesis and Electrochemical Behavior of Electroactive Bistetrathiafulvalene-attached Thiacalix[4]arene Assemblies

Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies（5a and 5b） formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones（3a and 3b） and 4,5-biscyanoethylthio-1,3-dithiole-2-one（4）. All the four new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones（3a and 3b） were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units（5a and 5b） were provided.

SYNTHESIS AND PROPERTIES OF POLYMERIC BIS (ETHYLENEDITHIO)-TETRATHIAFULVALENES

A polymer containing bis(ethylenedithio)-tetrathiafulvalene moiety was synthesized and its electrochemical properties were studied by cyclic voltammetry. The charge transfer complexes of the polymer with TCNQ and I//2 were obtained by chemical oxidation in dichlorobenzene. All of them are semi-conductors. A film of the polymer was obtained by casting. Its conductivity, after oxidation with iodine, is 2.24 multiplied by 10** minus **6S center dot cm** minus **1 and its conducting state is stable in air. (Author abstract) 10 Refs.

Amperometric Glucose Sensor with Tetrathiafulvalene as an Electron Transfer Mediator

glucose oxidase (GOD) electrode with tetrathiafulvalene(TTF) as an elec-tron transfer mediator is described. By means of Nafion, TTF was modified on aglassy carbon(GC) electrode surface, and glucose oxidase was then immobilized onthe TTF-Nafion film, forming a GOD-TTF-Nafion enzyme electrode. Characteris-tics of the sensor are shown by cyclic voltammetry and constant potential measure-ments. The sensor responds rapidly to glucose, the time required to reach 95% ofthe steady-state current is less than 60s. The sensor displays a sensitive catalyticcurrent response to glucose and can be operated in a potential range in which theoxidation of common interfering species, such as ascorbic acid and uric acid, doesnot occur. The sensor is stable for more than 30 days at 4℃ and plasma glucose assays were correlated with spectrophotometry(,i = 10 , r= 0. 995).

Synthesis,structure and physical properties of the one-dimensional chain complex of tetrathiafulvalene carboxylate

A new Co(II) coordination polymer bearing TTF carboxylate group, [{Co2(trioTTF)2(H2O)6}·5H2O]n (1) (trioTTF = 2-(5,6,8,9,11,12,14,15-octahydro-[1,3]dithiolo[4,5-h][1,4,13,7,10]trioxadithiacyclopentadecin-2-ylidene)-1,3-dithiole-4,5-dicarboxylate), has been prepared and characterized. In the structure of 1, shorter intermolecular S····S contacts (3.565 ?) are found between the trioTTF groups from neighboring chains. The electric conductivity of 1 is poor due to the bulky crown-ether group, but it exhibits ferromagnetic interaction at low temperature.

Tetrathiafulvalene (TTF)-based gelators:Stimuli responsive gels and conducting nanostructures

Tetrathiafulvalene (TTF) and its derivatives have been intensively investigated for conducting materials for more than 30 years.As π-electron donors,TTF and its derivatives can be reversibly transformed into the respective TTF.+ and TTF2+.Due to its reversible feature,the TTF unit has been widely employed as the building block for switchable systems.In recent years studies of conducting nanostructures of TTF derivatives have received more and more attention.One simple way to prepare nano-structures is through the gelation processes.In this review,we have discussed recent progress in stimuli-responsive gels and conducting nanostructures based on TTF-based gelators.

Three Dimensional Sulfur-doped Graphene Hydrogels with Tetrathiafulvalene for High Performance Supercapacitors

By using tetrathiafulvalene as reducing and doping agents, three-dimensional （3D） sulfur-doped graphene hydrogels （SGHs） were facilely prepared in mixed solvents of dimethyl formamide and water. Several investigations reveal that TTF plays a critical role in the formation of such unique 3D architecture, as it not only reduces GO to self-assembly into 3D structures, but also can be transformed to TTF^·＋ and TTF^2＋ as doping agents in the reduction process. The morphology, crystal structure, chemical bonding, elemental composition and porosity of the as-prepared SGHs have been studied. Benefiting from well-defined and cross-linked 3D porous network architectures, the supercapacitors based on the SGHs in KOH 212.5 F·g^-1 at 0.3 A·g^-1. Furthermore, this capacitance also degree of reversibility in the repetitive charge/discharge cycling electrolyte exhibited a high specific capacitance of showed good electrochemical stability and a high test.

A Clicked Tetrathiafulvalene-oxyquinoline Dyad as an Optical and Electrochemical Zn2＋ Probe

A novel clicked tetrathiafulvalene derivative 3 bearing two 8-oxyquinoline groups was synthesized for the selective detection of Zn2＋ through optical and electrochemical changes. The addition of Zn2＋ and Cd2＋ induced a significant change in fluorescence intensity, which was attributable to the chelation-enhanced fluorescence effect from the oxyquinoline and 1,2,3-triazole rings. The electrochemical potentials of 3 in the presence of the Zn2＋ were shifted toward more positive values relative to those of the other metal cations tested.

Photophysical Properties and Photoinduced Electron Transfer between [60] Fullerene-Containing Cyclic Sulphoxide [C_(60)-C_6H_8SO] and Tetrathiafulvalene (TTF) by Laser Flash Photolysis

Photoinduced electron transfer (PET) processes between C 60-C 6H 8SO and Tetrathiafulvalene (TTF) have been studied by nanosecond laser photolysis. Quantum yields (Φ et) and rate constants of electron transfer (k et) from TTF to excited triplet state of fullerene-containing cyclic sulphoxide in benzonitrile (BN) have been evaluated by observing the transient absorption bands in the NIR region. With the decay of excited triplet state of fullerene-containing cyclic sulphoxide, the rise of radical anion of fullerene-containing cyclic sulphoxide is observed.

Colorimetric and electrochemical Pb^(2+) detection by imine-bridged tetrathiafulvalene-pyridine derivatives

Imine-bridged TTF-π-pyridine derivatives, 2NTTF, 3NTTF and 4NTTF, were synthesized and the cation-binding study was performed. It is noted that with the addition of the micromolar concentration of Pb2+ to the solution, these compounds display remarkable changes in solution color, 1H NMR spectra and electrochemical properties. The nitrogen atom of the imine-bridge in 2NTTF not only serves as a π-conjugated spacer but also participates in the sensing and coordinating properties.

Hydrogen bonding networks controllable by the substitution position of tetrathiafulvalene on the pyridine ring

Tetrathiafulvalene(TTF), as a classical building unit, has attracted considerable attention, especially its functional derivatives. Hydrogen bonding(H-bonding) networks are a class of traditional and stable nanostructures, which play an important role in two-dimensional self-assembly and multi-component co-assembly. In this paper, we studied the regulation of H-bonding networks by functional groups in TTF derivatives. The results indicate that the position of pyridine on TTF not only affects their self-assembly structures in different solvents, but also controls the H-bonding networks through different mechanisms. Both para-TTF and meta-TTF molecules show different co-assembled structures with solvents depending on whether or not the presence of carboxylic acid group. On the pre-prepared H-bonding networks formed by famous 1,3,5-tris(10-carboxydecyloxy)-benzene(TCDB) molecule, both para-TTF and meta-TTF disturbed the original network structures with different degree of TCDB deformation. The formed new H-bonding networks with or without TTF derivatives participation are mainly attributed to the position of pyridine in TTF-based molecules. These results would be important for design of exceptional and functional nanostructures starting with the design of building block.

Organic Field-effect Transistors Based on Tetrathiafulvalene Derivatives

1 Restults Tetrathiafulvalene (TTF) and its derivatives have been extensively investigated in the field of organic conductors and superconductors since 1973. Recently, their application in organic field-effect transistors (OFETs) has attracted considerable attention. So far, on the one hand, the fabrication techniques of the TTF-based FETs have been primarily limited to high vacuum evaporation, which is a relatively expensive process. On the other hand, low FET performances, such as the low on/off ratio...

Novel clicked tetrathiafulvalene-calix[4]arene assemblies:Synthesis and intermolecular electron transfer toward p-chloranil

Two tetrathiafulvalene-calix[4]arene assemblies （TTF-calix-1 and TFF-calix-2） have been synthesized by the click reaction. Both their cyclic voltammograms show, as expected, two one-electron quasi- reversible redox behavior. The UV-vis absorption spectra studies show that these two assemblies undergo progressive oxidation at the TFF moiety in presence of increasing amounts of Cu2＋ or Hg2＋. Moreover, the absorption studies show intermolecular electron transfer between compounds TrF-calix- I or TI＇F-calix-2 and p-chloranil may be promoted by specific metal ions such as Pb2＋, Sc3＋ etc.

Supramolecular conducting microfibers from amphiphilic tetrathiafulvalene-based organogelator

An amphiphilic tetrathiafulvalene molecule was designed and readily synthesized. The am-TTF can gelate a variety of organic solvents in view of multiple intermolecular interactions, especially in polar solvent.SEM observation provided clear evidence for the self-assembled micro/nanofibers morphologies in gelation state. Moreover, XRD measurements indicated the formation of highly-ordered columnar structures. The FT-IR spectra revealed that the formation of mixed-valence states with the absorption over 1700 cm^(-1), showing the semiconductive behaviors with the conductivity of 10^(-4)S/cm. The am-TTF based conducting fibers could be promising candidates for organic electronics.

Synthesis and properties of tetrathiafulvalene-porphyrin assemblies

Two donor-σ-acceptor molecular systems incorporating tetrathiafulvalene(TTF)and tetraphenylpor-phyrin(TPP)units,TTF-TPP(dyad 1)and TTF-TPP-TTF(triad 2),were synthesized.Both dyad 1 and triad 2 and their synthetic intermediates have been characterized by 1H nuclear magnetic resonance(1H NMR)and mass spectro-graphy(MS).Their ultraviolet and visible spectroscopy(UV-Vis)and cyclic voltammetry(CV)showed negligible intramolecular charge transfer interaction in their ground states.Theirfluorescence intensity was strongly quenched compared with TPP,which implied the photoinduced electron transfer occurred from the TTF unit to the TPP unit in the excited state.On the other hand,theirfluorescence intensity could be modulated by sequential oxidation of the TTF unit using chemical methods,which exhibited their potential application influorescence molecular switch.

Spectroscopic and electrochemical studies on molecular recognition of tetrathiafulvalene derivative with P-glycoprotein and drug-resistant leukemia cells

Cancer is still one of the important diseases that threatens the health of people. Multidrug resistance(MDR) is the main factor that leads to the failure of cancer chemotherapy. Thus, MDR diagnosis could facilitate the monitoring of the therapy process and realization of efficient treatment of tumors. In this study, we have tried to use a new tetrathiafulvalene(TTF) derivative(TTF-(COONBu4)2) to sensitively recognize the MDR through the multi-signal responsive strategy. The relevant electrochemical and spectroscopic studies demonstrate the specific binding behavior of TTF-(COONBu4)2 with P-glycoprotein(P-gp) as well as drug-resistant leukemia cells. Especially due to the over-expression of specific components of P-gp on the plasma membranes of drug resistant cells, the electrochemical and hydrophilic/hydrophobic features of drug resistant-leukemia cells are apparently different from those of other kinds of leukemia cells. Meanwhile, Fourier transform infrared spectroscopic study illustrates that the most intense vibration band of TTF moieties in the 1400–1600 cm-1 range is almost smeared out upon binding to P-gp, and the binding of TTF-(COONBu4)2 to P-gp may also lead to changes in protein secondary structure and backbone. This observation may advance the development of the new TTF agent for the promising clinical diagnosis and monitoring of MDR of tumors with the aim of successful chemotherapy for human cancer.

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Two donor-σ-acceptor molecules containing tetrathiafulvalene(TTF)and carbazole moieties were synthesized bythe reactionof 9-(4-bromo-butyl)-carbazole(1)with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7-(methylthio)-tetrathiafulvalene(2)or2,6-bis(2-cyanoethylthio)-3,7-bis(methylthio)tetrathiafulvalene(3)in the presence of CsOH·H_(2)O,respectively.The structures of the molecules were characterized by 1 H NMR,13 C NMR,MS,and elemental analyses.They showed negligible intramolecu-lar charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results.Compared with carbazole,their fluorescence was strongly quenched,which implied that a photo induced electron transfer(PET)interaction between TTF and carbazole moieties occurred.

Synthesis and Characterization of Donor-Acceptor-Donor Triads Containing Tetrathiafulvalene and Naphthalene Diimide Units: Towards Regulation of the Intermolecular Charge-Transfer Interaction by Varying the Attached Side Groups

A series of donor-acceptor-donor triads 16 consisting of tetrathiafulvalene and naphthalene diimide units were synthesized and characterized. UV/Vis spectroscopic and cyclic voltammetric studies indicate that these triads show negligible intramolecular charge transfer interaction in the ground state. In contrast to that of the reference compound 36, their fluorescence intensities were reduced in the following sequences: 3≈4≈5≈6<1≈2, which is probably due to photoinduced electron transfer in triads 16. Two solid forms (yellow and green) of triads 15 were obtained, while only green form for triad 6 was obtained under the same conditions. Studies of the yellow and green forms with UV, XRD and DSC were performed. It was suggested that varying the attached side groups may regulate intermolecular charge transfer interactions in the solid state.

Synthesis of tetrathiafulvalene C_(60)Br_n and their Langmuir films

Buckminsterfullerene (C60) was found to be the third form of carbon in 1985. Themethod for the macroscale synthesis of C60 has been developed successfully. C60 has at-tracted great attention owing to its particular physical and chemical properties. Obeng et al. reported the molecular behavior of C60 at the air-water interface andfound that it was difficult to obtain good quality LB films. It arose from its rigidityand hydrophobicity. We found that C60Brn could form stable mononlayers at

Construction of Tetrathiafulvalene-based Covalent Organic Frameworks for Superior Iodine Capture

The effective capture of radioiodine species during nuclear fuel reprocessing and nuclear accidents is of primary importance but remains challenging for the sustainable development of nuclear energy.Herein,we report two newly designed two-dimensional(2D)and three-dimensional(3D)covalent organic frameworks by introducing tetrathiafulvalene functional groups into the building units for the simultaneous physisorption and chemisorption capture of iodine molecules.Remarkably,the obtained 3D TTF-TAPT-COF material exhibited a superior iodine vapor adsorption capacity of up to 5.02 g/g at 348 K and under ambient pressure and an adsorption kinetics of 0.515 g/(g∙h),surpassing most of other materials reported so far.The strong physiochemical interactions between iodine molecules and the frameworks of the obtained COFs were revealed by a set of experimental techniques.This study provides a feasible approach for the rational design and the construction of novel and effective COF-based adsorbents for iodine enrichment and related environmental remediation.

Halogen-bonded Cocrystal Based on Tetrathiafulvalene Derivatives

In this paper, two cocrystals 1 and 2 with the same chemical composition [L1.L2 ](L1 = bis(4’-pyridyl)-TTF, L2 = 4,4’-diiodophenyl) were synthesized by slow diffusion with different solvent systems. Cocrystals 1 and 2 were characterized by single-crystal X-ray and the purity of these two cocrystals was confirmed by PXRD data. The photocurrent responses of these two cocrystals were also tested. Only cocrystal 1 could generate photocurrent signal when exposed to light. From the crystal structure analysis, the possible reason may come from the different biphenyl conformations in L2.