Synthesis of new electron-donor compounds: Bis(2-thia-1,3-propylenedithio)teterathiafulvalene and bis(2-oxo-1,3-propylenedithio)tetrathiafulvalene

1,3-Dithiole-2-thione derivatives, which are starting compounds for the synthesis of new electron donors of the tetrathiafulvalene class, viz., bis(2-thia-1,3-propylendithio)tetrathiafulvalene and bis(2-oxo-1,3-propylendithio)tetrathiafulvalene, were obtained by the reaction of bis(tetraalkylamonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)zincates with 1,3-dichlorodimethyl sulfide and 1,3- dibromoacetone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 471–474, April, 1990.     

新型I型五聚四硫富瓦烯衍生物的合成和性质

利用2,3-二(2'-氰乙基硫基)-6,7-二烷硫基四硫富瓦烯在甲醇钠的作用下消除一个保护基团生成四硫富瓦烯单钠盐,与1,4-二(氯甲基)苯反应,形成单桥-双(四硫富瓦烯)衍生物,生成的单桥-双(四硫富瓦烯)衍生物再次在甲醇钠的作用下消除剩下的保护基团,形成单桥-双(四硫富瓦烯)衍生物二钠盐,最后与四(3'-碘丙硫基)四硫富瓦烯反应形成新型I型五聚TTF衍生物,并通过循环伏安法和化学氧化法分别对其氧化还原性质和紫外光谱进行了研究.     

新型I型五聚四硫富瓦烯衍生物的合成和性质

利用2,3-二(2'-氰乙基硫基)-6,7-二烷硫基四硫富瓦烯在甲醇钠的作用下消除一个保护基团生成四硫富瓦烯单钠盐,与1,4-二(氯甲基)苯反应, 形成单桥-双(四硫富瓦烯)衍生物, 生成的单桥-双(四硫富瓦烯)衍生物再次在甲醇钠的作用下消除剩下的保护基团, 形成单桥-双(四硫富瓦烯)衍生物二钠盐, 最后与四(3'-碘丙硫基)四硫富瓦烯反应形成新型I型五聚TTF衍生物, 并通过循环伏安法和化学氧化法分别对其氧化还原性质和紫外光谱进行了研究.     

Bis(dithiomethyl-tetrathiafulvalene) with two phenyl-phosphino bridges

The single crystal X-ray structure of the precursor dithiomethyl-tetrathiafulvalene (MeS)₂TTF is reported, together with theoretical calculations at DFT level, which afforded two energy minima corresponding to cis and trans orientations of the thiomethyl substituents. The bis(tetrathiafulvalene) reaction of this TTF derivative followed by the reaction with phenyldichlorophosphine provides a new rigid bis(tetrathiafulvalene [TTF]) containing a 1,4-dihydro-1,4-diphosphinine ring between the two redox active units. Its solid-state structure, determined by single crystal X-ray diffraction analysis, shows the coexistence of both cis and trans isomers. Cyclic voltammetry measurements are in accordance with the existence of a communication between the two TTFs, as illustrated by the splitting of the oxidation waves.     

Optical properties of bis(pyrazino)tetrathiafulvalene salts

The optical reflectance and absorption spectra of (BPTTF)₂BF₄[where BPTTF is bis(pyrazino) tetrathiafulvalene] and similar salts are reported for a wide spectral region.     

二-(亚乙基-二硫)-四硫富瓦烯侧基聚合物的合成及表征

二 （亚乙基 二硫） 四硫富瓦烯侧基聚合物的合成及表征秦伟朱道本（中国科学院化学研究所有机固体开放研究实验室北京１０００８０）关键词聚乙炔，导电性，ＥＴ衍生物自８０年代初期发现第一个有机超导体以来，至今已发现了近５０种有机超导体［１］，超导转变温度...     

双（亚烷二硫基)四硫富瓦烯衍生物的合成及其电化学性质

以四(氰乙硫基)四硫富瓦烯为原料经醇钠消去氰乙基生成四硫富瓦烯四硫盐， 再与二元卤代烷烃化反应，除了得到三种文献报道的双(亚烷二硫基)四硫富瓦烯衍 生物外，还得到三种新的“四桥”双—四硫富瓦烯衍生物，为“桥式”双—四硫富 瓦烯衍生物的合成提出了一种新的方法．并研究了它们的循环伏安图、电化学性质 和紫外—可见光光谱．     

A chirality-induced alpha phase and a novel molecular magnetic metal in the BEDT-TTF/tris(croconate)ferrate(III) hybrid molecular system

The novel paramagnetic and chiral anion [Fe(C5O5)3]3- has been combined with the organic donor BEDT-TTF (= ET = bis(ethylenedithio)tetrathiafulvalene) to yield the first chirality-induced alpha phase and a paramagnetic metal.     

“桥式”双四硫富瓦烯衍生物的合成及电化学行为

循环伏安法;紫外-可见光谱法;“桥式”双四硫富瓦烯衍生物的合成及电化学行为     

Electroconducting Radical-Cation Salts Based on Tetrathiafulvalene Derivatives and Transition Metals Bis(dicarbollides)

Russian Journal of General Chemistry - The radical-cationic salts based on tetrathiafulvalene derivatives and bis(dicarbollide) transition metal complexes [3,3′-M(1,2-C2B9H11)2]? (M =...     

A facile synthesis of linear benzene-fused bis(tetrathiafulvalene) compounds and their application for organic field-effect transistors

Three new linear benzene-fused bis(tetrathiafulvalene) compounds (1-3) were easily synthesized by one-step phosphite-induced cross-coupling reactions; a solution processed organic field-effect transistor based on 2 shows high mobility of 0.02 cm2/Vs.     

Bis(tetrathiafulvalene)-calix[2]pyrrole[2]- thiophene and its complexation with TCNQ

The synthesis of a rare example of a calix[2]pyrrole[2]thiophene derivative incorporating two tetrathiafulvalene units is described along with its X-ray crystal structure. Complexation studies between the bis(tetrathiafulvalene)-calix[2]pyrrole[2]thiophene and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) were carried out in solution using absorption and ESR spectroscopies as well as in the solid state using X-ray crystallography and IR spectroscopy.     

A metal-directed self-assembled electroactive cage with bis(pyrrolo)tetrathiafulvalene (BPTTF) side walls

A straightforward synthesis of a bis(pyrrolo)tetrathiafulvalene (BPTTF)-based tetratopic ligand bearing four pyridyl units is described. The first example of a TTF-based self-assembled cage has been produced from this redox-active ligand through metal-directed synthesis with a cis-coordinated square-planar Pt(II) complex. The resulting cage corresponds to a trigonal-prismatic structure, as shown by X-ray crystallography. A UV-vis titration indicated that the electron-rich cavity can be used to incorporate one molecule of tetrafluorotetracyano-p-quinodimethane (TCNQF(4)).     

The Inorganic-free Organic Conductor α''''-(ET)_2C_6H_4(SO_3)_2 : Its Synthesis, Structure, and Conductivity

Having more than twenty years?glory, ET series still keep the most promising family in various kinds of organic conductors. Most of ET based molecular conductors consist of organic cationic ET+0.5 radical and certain anionic inorganic component such as the superconductor k-(ET)2Cu[N(CN)2]Cl (TC = 12.8K, 0.3kbar)1. Recently, the first purely organic superconductor b-(ET)2SF5CH2CF2SO3 (TC = 5.2K)2 has been reported, which aroused our interest on this kind of inorganic-free organic c…     

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 χ.     

Preparation and crystal structure of dual-functional precursor complex bis(acetylacetonato)nickel(II) with 4-pyridyltetrathiafulvalene

A tetrathiafulvalene (TTF) derivative 4-pyridyltetrathiafulvalene (Py-TTF) was synthesized. The 1:2 Ni complex 1 of bis(acetylacetonato)nickel(II) coordinated with Py-TTF was prepared. Complex 1 crystallizes in the monoclinic space group P2(1)/c. Two pyridyl N atoms from two different molecules of Py-TTF are coordinated in the trans configuration to the Ni ion of Ni(acac)2 to form an octahedral Ni complex, which is a precursor for both conducting and magnetic materials.     

Bimetallamacrocycles involving tetrakis(diphenylphosphinoalkylthio)tetrathiafulvalene

Two novel tetrathiafulvalene (TTF) ligands, substituted by four diphenylphosphinoalkylthio groups, have been synthesized and characterized. Their redox properties, determined by cyclic voltammetry, have been compared with their precursors and discussed. The ability of these redox active ligands to react with two equivalent of cis-W(CO)₄(C₅H₁₁N)₂ is presented. X-ray crystal structure of a bis 13-metallamacrocycle is reported together with its redox behaviour.     

Synthesis,structure and electrochemical properties of two new unsymmetrical tetrathiafulvalene derivatives

Two new unsymmetrical tetrathiafulvalene (TTF) derivatives, 2,3‐bis(cyanoethylthio)‐6,7‐(methyl‐ethylenedithio)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.     

3,4‐[2,2‐Bis(methoxyethoxymethoxymethyl)propylenedithio]‐3′,4′‐(ethylenedithio)tetrathiafulvalene: a spiro‐substituted BEDT–TTF analogue

The crystal structure of the title compound [systematic name: 2‐(1,3‐dithiolo[4,5‐b][1,4]dithiin‐2‐ylidene)‐6,6‐bis(methoxyethoxymethoxymethyl)‐1,3‐dithiolo[4,5‐b][1,4]dithiepine], C₂₁H₃₀O₆S₈, a spiro‐substituted BEDT–TTF analogue [BEDT–TTF is bis(ethylenedithio)tetrathiafulvalene], has a strongly bent heterocyclic framework. The seven‐membered ring adopts a pseudo‐chair conformation with notably widened ring bond angles, especially at the methylene C atoms [119.49 (11) and 117.60 (11)°]. The axial side chain adopts an extended conformation, but the equatorial side chain curls back on itself and the O atom nearest the ring system is involved in three short contacts to H atoms (2.45–2.53 Å). The molecules pack in centrosymmetrically related pairs, which are isolated from each other by columns of the polyether side chains. This study emphasizes the ease of distortion of the neutral bis(propylenedithio)tetrathiafulvalene ring structure, and how the need to accommodate side chains can easily override the tendency of these donor systems to form stacks in the crystalline state.     

Synthesis of 1,3-dithiole-2-thiones and tetrathiafulvalenes using oligo-(1,3-dithiole-2,4,5-trithione). (Review)

Methods for the synthesis of 1,3-dithiole-2-thiones, based on [4+2] cycloaddition of the 1,3-dithiole-2,4,5-trithione oligomer to various unsaturated acyclic, carbocyclic, and heterocyclic compounds, are reviewed. Methods for the production of substituted tetrathiafulvalenes, which can be regarded as derivatives of bis(ethylenedithio)tetrathiafulvalene, from 1,3-dithiole-2-thiones synthesized by this method are described. Dedicated to the memory of Professor O. Neilands. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 483–502, April, 2006.