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.

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 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.

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.

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.

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.

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.

Synthesis and electrochemical properties of a chiral silyl-substituted tetrathiafulvalene derivative

A new chiral tetrathiafulvalene （TTF） derivative and related silyl-substituted 1,3-dithiole-2-（thi）one compounds were synthesized and characterized by 1H NMR, 13C NMR, MS and IR spectra. Single crystal structure of the silyl-substituted 1,3-dithiole-2-one revealed the high degree of conjugation of the five- membered ring moiety in the compound. The electrochemical properties of the new TTF derivative were studied by cyclic voltammetry and the results indicated that the electron-donating ability of the chiral TI＂F derivative was similar to that of BEDT-TTF. The AE value for the new TTF derivative was smaller than those for TTF and BEDT-TrF, indicative of decreased Coulombic repulsion in the dicationic redox state. Formation of charge-transfer （CT） complex between the new donor and electron acceptor 2,3-dichloro-5,6-dicvano-1,4-benzocluinone （DDO） was demonstrated.

The Synthesis of Third-order Optical Nonlinear Organic Polyheterocyclic Materials

Synthesis of the third-order nonlinear materials: bis (1,4-dihydroxynaphthalene) tetrathiafulvalene and bis (1,4-dialkoxylnaphthalene) tetrathiafulvalene has been achieved in four steps, starting from 2,3-dichloro-1,4-naphthaquinone. The materials exhibit larger third-order nonlinear optical susceptibilities c(3) .

Effect of the protection layer formed by cross-linked gelatin on the stability and performance of glucose and oxygen fuel cells

A glucose oxidation catalyst comprising carbon nanotube,tetrathiafulvalene(TTF),gelatin,glutaraldehyde(GA)and glucose oxidase(GOx)(CNT/[TTF-GOx]/Gelatin+GA)is suggested to enhance the reactivity of glucose oxidation reaction(GOR),and the performance and stability of enzymatic biofuel cells(EBCs)using this catalyst.In this catalyst,TTF is used as mediator to transfer electron effectively,while GA is crosslinked to gelatin to form non-soluble network.The structure prevents the dissolution of gelatin from aqueous electrolyte and reduces the leaching-out of GOx and TTF molecules.To confirm the crosslinking effect of GA and gelatin,Fourier-transform infrared spectroscopy(FT-IR)and electrochemical evaluations are utilized.According to FT-IR analysis,it was observed that the amide I peak shifted after crosslinking.This is evidence showing the appropriate network formation and the reactivity of CNT/[TTFGOx]/Gelatin+GA is well preserved even after multiple potential cycling.In addition,its GOx activity is regularly monitored for one month and the measurements prove that the structure prevents the leaching out of GOx molecules.Based on that,EBC using the anodic catalyst shows excellent performances,such as open circuit voltage of 0.75 V and maximum power density of 184μW/cm^(2).