在Cs OH的CH3OH/DMF溶液中,4,5-二(氰乙硫基)乙二硫撑四硫富瓦烯(1a),4,5-二(氰乙硫基)甲基乙二硫撑四硫富瓦烯(1b),4,5-二(氰乙硫基)丙二硫撑四硫富瓦烯(1c)和4,5-二(氰乙硫基)苯基四硫富瓦烯(2)分别与五(乙二醇醚)二-对甲苯磺酸盐经偶联反应合成了4个新型的非对称四硫富瓦烯环状冠醚衍生物(3a~3c和4),其结构经1H NMR,~(13)C NMR,ESI-MS和元素分析表征。用循环伏安法研究了3a~3c和4对碱金属离子(Na+,Li+,K+和Rb+)的响应性能。结果表明:2,3-二硫-(3',6',9',12'-四氧冠醚)-6,7-丙二硫代四硫富瓦烯(3c)和2,3-二硫-(3',6',9',12'-四氧冠醚)-6,7-苯基四硫富瓦烯(4)对Na+响应较明显,其△E1/21分别为30 m V和45 m V。 相似文献
A new chiral tetrathiafulvalene(TTF) derivative and related silyl-substituted 1,3-dithiole-2-(thi)one compounds were synthesized and characterized by ~1H NMR,~(13)C 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 fivemembered 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 TTF derivative was similar to that of BEDT-TTF.The △E value for the new TTF derivative was smaller than those for TTF and BEDT-TTF,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-dicyano-l,4-benzoquinone(DDQ) was demonstrated. 相似文献
Tetrathiafulvalene (TTF) monolayers covalently bound to oxide-free hydrogen-terminated Si(100) surfaces have been prepared from the hydrosilylation reaction involving a TTF-terminated ethyne derivative. FTIR spectroscopy characterization using similarly modified porous Si(100) substrates revealed the presence of vibration bands assigned to the immobilized TTF rings and the Si-C═C- interfacial bonds. Cyclic voltammetry measurements showed the presence of two reversible one-electron systems ascribed to TTF/TTF(.+) and TTF(.+)/TTF(2+) redox couples at ca. 0.40 and 0.75 V vs SCE, respectively, which compare well with the values determined for the electroactive molecule in solution. The amount of immobilized TTF units could be varied in the range from 1.7 × 10(-10) to 5.2 × 10(-10) mol cm(-2) by diluting the TTF-terminated chains with inert n-decenyl chains. The highest coverage obtained for the single-component monolayer is consistent with a densely packed TTF monolayer. 相似文献
A protonated bifunctional pyridine-based tetrathiafulvalene (TTF) derivative (DMT-TTF-pyH)NO3 and a copper(II) complex Cu(acac)2(DMT-TTF-py)2 have been obtained and studied. Electronic spectra of the protonated compound show a large ICT (intramolecular charge transfer) band shift (Deltalambda=136 nm) compared with that of the neutral compound. Cyclic voltammetry also shows a large shift of the redox potentials (DeltaE1/2(1)=77 mV). Theoretical calculation suggests that the pyridium substituent is a strong pi-electron acceptor. Crystal structures of the protonated compound and the metal complex have been obtained. The dihedral angle between least-squares planes of the pyridyl group and the dithiole ring might reflect the intensity of the ICT effect between the TTF moiety and the pyridyl group. It is also noteworthy that the TTF moiety could be oxidized to TTF2+ dication by Fe(ClO4)(3).6H2O when forming a metal complex, while the protonated TTF derivative can only be oxidized to the TTF*+ radical cation by Fe(ClO4)(3).6H2O even with an excess amount of the Fe(III) salt, which can be used to control the oxidation process to obtain neutral TTF, TTF*+ radical cation, or TTF2+ dication. 相似文献
The synthesis of new S(2)O(4)-crown annelated tetrathiafulvalene (TTF) derivatives substituted with one terminal thiol group is described. Self-assembled monolayers (SAMs) of these compounds have been assembled on gold and platinum surfaces, the latter substrate giving improved quality films. SAMs of TTF derivative 16b are the most stable of those we have studied. Electrochemical data for SAMs of 5a, 5b, 8, 16a, and 16b in acetonitrile reveal two reversible one-electron waves, typical of the TTF system; the current increased linearly with scan rate, indicating a surface wave response. SAMs of 8, 16a, and 16b exhibited an electrochemical response in aqueous electrolytes, which was observed between 50 and 100 cycles. Moreover, if the potential scanned was limited to the first TTF oxidation, the cyclic voltammetry response was observed for at least 1000 cycles. Metal complexation by the crown ionophore of the SAMs in acetonitrile has been monitored by a positive shift in the first oxidation potential of the TTF unit (maximum DeltaE(1)(1/2) = 80 mV for Ag(+)). We also report the X-ray crystal structure of TTF-crown derivative 21 bearing two hydroxymethyl substituents, synthesized during the course of this work. The structure is characterized by infinite chains of molecules linked by strong intrachain hydrogen bonds between the terminal hydroxy groups. 相似文献
Tetrathiafulvalene (TTF) derivative substituted with two butyl- and two dodecylthiol chains is adsorbed on polycrystalline gold. The TTF-derived thiol adsorbates were characterized by ellipsometry, contact angle goniometry, infrared and X-ray photoelectron spectroscopy and cyclic voltammetry. The molecule is strongly anchored on the gold surface through the sulfur terminating the alkylthiol chains. On the average, the TTF moiety is oriented extended away from the gold surface. The topmost layer of the film containing the dibutyl chains is disordered with gauche defects. The molecule was organized with majority of the alkylthiol chains bound to the gold surface. There are indications of pinholes in the monolayer due to steric hindrance of the bulky TTF rings. The molecular systems consisting of an electroactive pi-system such as TTF, are promising for thin-film field effect transistor application. 相似文献
In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins. 相似文献
CT or not CT : Three imidazole‐annulated TTF derivatives 1 – 3 have been prepared and fully characterized. The influence of the TTF unit on the pKa values of the acceptor units as determined by photometric titration has been discussed. The results reported here are part of an initial exploratory study to generate a range of well‐defined coordination networks.
[structure: see text] [60]Fullerene was functionalized with a TTF derivative and a bis-mesogenic fragment. The synthetic methodology was based on the addition of a malonate derivative to C60 (Bingel-type reaction). Both the malonate and dyad showed smectic B and A phases. The supramolecular organization within the smectic layers was of the monolayer type for the malonate and of the bilayer type for the fullerene derivative. In the latter case, the supramolecular organization was governed by the C60 unit. 相似文献
A bis(diamino-diamido) tetrathiafulvalene (TTF) derivative H(4)L(2) has been designed and synthesized. Experiments of pH titration reveal that integrating the redox active TTF unit with the diamino-diamido moiety adds new properties to the traditional ligand. Oxidation of the TTF moiety increases the acidity of the amido group, and the coordination of metal ions is also sensitive to the oxidation state of the ligand. This compound is capable of acting as a leaving or accepting ligand for proton and metal ions. The electrochemistry of the protonated TTF derivative of H(4)L(2) was studied in the presence of a series of oxo anions and metal cations. The results indicate that the redox potentials selectively respond to HC(2)O(4)(-) and SO(4)(2-) anions, and Ni(II) and Cu(II) cations. Solid-state structures of a cation-anion salt H(8)L(2)·2SO(4)·8H(2)O and a nickel coordination compound [Ni(2)L(2)]·2DMF have been characterized by means of X-ray crystallography which are helpful in understanding the inter-ion interactions. 相似文献