二苯并四硫代富瓦烯类衍生物的合成和电化学行为

合成了四个二苯并四硫代富瓦烯(DB-TTF)的衍生物(3a～b, 4a～b), 给出了它们的核磁共振氢谱和碳谱, 质谱,紫外吸收光谱及元素分析等数据. 用=循环伏安法测定了它们的氧化电位, 并将此与DB-TTF的氧化电位作了比较.发现: 两端取代的硫酮基对分子体系的吸电子效应较强,会明显增大分子的第一氧化电位 , 而且会降低分子内的Coulomb作用力, 相比之下, 在四周顶点上取代的烷氧基对分子体系的给电子效应较弱.     

不对称四硫富瓦烯衍生物合成新方法及其电化学性质的研究

以2,3－二（2′－氰乙硫基）－6,7－亚烷硫基四硫富瓦烯为原料,在醇钠的作用下消去氰乙基生成的二元硫负离子与对－二（氯甲基）苯反应除了生成两种新的不对称四硫富瓦烯衍生物外,还得到两种新的“二桥”－双四硫富瓦烯衍生物,为四硫富瓦烯衍生物的合成提供了一种新的方法。并对不对称四硫富瓦烯衍生物和“二桥”－双四硫富瓦烯衍生物的循环伏安图、电化学性质和UV－Vis光谱进行了研究。     

双(6,7-二甲硫基四硫富瓦烯-2,3-二硫)金属配合物的合成

以6，7－二甲硫基四硫富瓦烯－2，3－二硫盐为配体合成了3种未见文献报道的双（6，7－二甲硫基四硫富瓦烯－2，3－二硫）金属配合物，为“桥式”四硫富瓦烯衍生物的合成创造出一种新方法，并对只得到中性产物提出了合理的解释。研究了其IR及室温电导率。     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

X-ray structure of the organic conductor (ET)8[Hg2Br6·PhBr]2

The electrochemical oxidation of ET [bis(ethylenedithio)tetrathiafulvalene] in bromobenzene (electrolyte Bu ₄ N[HgBr ₃ ]) gave the radical-cation salt (ET) ₈ [Hg ₂ Br ₆ ·PhBr] ₂ (1), a new organic metal with a temperature range of 300–125 K. At 125 K a metal—dielectric transition is observed. Crystallographic data for (1):a=19.171(6),b=12.668(4),c=17.777(6) Å, =118.03(3), =89.45(2), =101.21(3)°, P ,Z=1,d _calc=2.30 g/cm ³ . The crystal structure of (1) is laminar. In the conducting organic layer the ET radical cations are linked into bands by shortened intermolecular S···S contacts of the side-to-side type. The anionic layer consists of centrosymmetric complexes [Hg ₂ Br ₆ ·C ₆ H ₅ Br] ₂ ^4– . The Hg ¹ and Hg ² atoms are characterized by a trigonal configuration of the Hg-Br bond which is built up, on account of secondary Hg···Br interactions, into trigonal-bipyramidal for Hg ¹ and trigonal-pyramidal (tetrahedral) for Hg ² . Interaction between the anionic and cationic layers is effected through Br ⁶ ...S ⁸ contacts [3.491(7) Å)].Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 894–902, April, 1992.     

Synthesis and crystal structure of an organic semiconductor (ET)4[Hg2I6]

A new cation-radical salt (ET)₄[Hg₂I₆] (1), where ET is bis(ethylenedithio)tetrathiafulvalene, has been synthesized in the system ET-HgI₃ ^–-PhCl. An X-ray study of 1 (a=41.02(5),b=23.01(1),c=8.233(2) Å,V=7772(3) ų, space groupPc2₁ b,Z=4,d _calc=2.308 g cm^–3) has established its composition, chemical formula, and the main structural features. The ET cation-radicals are packed in the conducting layer, the type of packing is ; the [Hg₂I₆]^2– anion has a dimeric structure. The temperature dependence of the conductivity of the (ET)₄[Hg₂I₆] crystals (₃₀₀=6 Ohm^–1 cm^–1) has a semiconducting character.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1240–1244, July, 1994.We thank M. G. Kaplunov for his participation in the discussion of the obtained results.This work was financially supported by the Scientific Council on the Problems of High-Temperature Superconductivity (Grant No. 90346 Metallorg) and the Russian Foundation for Basic Research (Project No. 93-02-2384).     

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．     

Reversible Guest Uptake/Release by Redox‐Controlled Assembly/Disassembly of a Coordination Cage

Controlling the guest expulsion process from a receptor is of critical importance in various fields. Several coordination cages have been recently designed for this purpose, based on various types of stimuli to induce the guest release. Herein, we report the first example of a redox‐triggered process from a coordination cage. The latter integrates a cavity, the panels of which are based on the extended tetrathiafulvalene unit (exTTF). The unique combination of electronic and conformational features of this framework (i.e. high π‐donating properties and drastic conformational changes upon oxidation) allows the reversible disassembly/reassembly of the redox‐active cavity upon chemical oxidation/reduction, respectively. This cage is able to bind the three‐dimensional B₁₂F₁₂^2? anion in a 1:2 host/guest stoichiometry. The reversible redox‐triggered disassembly of the cage could also be demonstrated in the case of the host–guest complex, offering a new option for guest‐delivering control.     

A Novel Poly(aryleneethynylene) with Tetrathiafulvalene (TTF) Side Chains: Synthesis,Self‐Assembly,and Electroactive Property

A novel poly(aryleneethynylene), in which the main chain and the tetrathiafulvalene (TTF) side chains are coplanar, has been prepared and characterized. The polymer can self‐assemble in tetrahydrofuran (THF) and the π‐extended coplanar backbones adopt good face‐to‐face stacking, which is confirmed by X‐ray diffraction (XRD) analysis. Cyclic voltammetry has revealed that the polymer has reversible electroactive properties. The optical bandgap deduced by UV‐vis absorption spectroscopy and the electrochemical bandgap are 2.03 and 2.14 eV. The conductivities of the powder and the realigning solid of the polymer are 6 × 10⁻⁸ and 4 × 10⁻⁶ S cm⁻¹.

     

TTF单元与苯单元构建的新型TTF环蕃的合成和性质

以4,5-二(2'-氰乙基硫基)-1,3-二硫杂环戊烯-2-硫酮为原料经甲醇钠消除一个氰乙基生成4-(2'-氰乙基硫基)-1,3-二硫杂环戊烯-2-硫酮的单钠盐, 生成的单钠盐再与1,4-二(氯甲基)苯反应生成4,4'-二(2-氰乙基硫基)-5,5'-(1,4-二亚甲基苯)-二(1,3-二硫杂环戊烯-2-硫酮). 接着在乙酸汞的作用下生成4,4'-二(2-氰乙基硫基)-5,5'-(1,4-二亚甲基苯)-二(1,3-二硫杂环戊烯-2-酮), 此化合物在亚磷酸三乙酯的作用下发生偶联反应, 生成由TTF单元和苯单元构建的新型四硫富瓦烯环蕃和另一种四硫富瓦烯衍生物. 并分别通过循环伏安法和化学氧化法对它们及其导电复合物的电化学性质和紫外光谱进行了研究. 还研究了这种新型四硫富瓦烯环蕃在金纳米颗粒表面自组装行为.