双-(二烷硫基四硫富瓦烯二硫)金属配合物的合成及性质研究

合成了三种未见文献报道的双-(二烷硫基四硫富瓦烯二硫)金属配合物和三种新的四硫富瓦烯(TTF)桥联的双金属配合物,测定了它们的导电率,讨论了含Ni配合物的电导率优于含Cu,Hg配合物的原因。     

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。     

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．     

富勒烯C60硫桥键联四硫富瓦烯衍生物的理论研究

利用半经验AM1法研究了富勒烯C₆₀硫桥键联四硫富瓦烯衍生物和富勒烯C₆₀键联四硫富瓦烯衍生物的几何构型,电子结构.计算结果显示,富勒烯C₆₀硫桥键联四硫富瓦烯衍生物的四硫富瓦烯(TTF)平面与C₆₀发生作用,使其弯曲的程度比富勒烯C₆₀键联四硫富瓦烯衍生物的大,从而形成一种独特的四硫富瓦烯(TTF)平面半包裹C₆₀的空间构型的D-A体系.这很可能是由于C-S单键的灵活性造成的.而且它们的HOMO轨道主要分布在四硫富瓦烯(TTF)部分,而LUMO轨道则主要分布在C₆₀上.预测了富勒烯C₆₀硫桥键联四硫富瓦烯衍生物很有可能在激发态下产生更长寿命的电荷分离态.     

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。     

四硫富瓦烯衍生物修饰的银溶胶

四硫富瓦烯衍生物修饰的银溶胶;银溶胶;纳米粒子;四硫富瓦烯;氧化还原;表面修饰     

烷硫基四硫富瓦烯的合成及其性质的研究

分别以 1 ,3,4 ,6-四硫代戊搭烯 -2 ,5-二酮和 4 ,5-二 ( 2′-氰基乙硫基 ) -1 ,3-二硫杂环戊烯 -2 -酮为原料 ,经偶联、醇解、烃化制得四甲硫基四硫富瓦烯和四乙硫基四硫富瓦烯。对两种方法制得产物的产率存在较大差别提出了合理的解释 ,并讨论了 2种四硫富瓦烯衍生物的循环伏安图及有关电化学性质。     

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.     

新型三(四硫富瓦烯)环蕃的合成和性质

利用四(3'-碘丙硫基)四硫富瓦烯和四硫富瓦烯二钠盐反应合成新的三(四硫富瓦烯)环蕃, 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.     

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.     

Spin-crossover behavior and electrical conduction property in iron(II) complexes with tetrathiafulvalene moieties

Iron(II) complexes with neutral and oxidized tetrathiafulvalene (TTF) moieties were prepared and X-ray crystallographic analyses, magnetic and electrical resistivity measurements suggested an interaction of spin transition and electrical conductivity.     

一类新型有机给体四硫代富瓦烯插烯物的合成与研究进展

概括了一类新型的有机电子给体－四硫代富瓦烯插烯物的合成方法，讨论了给体的循环伏安特性，并对其电荷转移复合物及自由基基阳离子盐的研究进展进行了简要的评述，参考文献４５篇。     

Molecular complexes based on tetrathiafulvalene and dialkylviologens

Three kinds of molecular complexes based on tetrathiafulvalene (TTF) and dialkylviologens were prepared and their crystal structures elucidated. While TTF-dimethylviologen complex forms a mixed stack arrangement of donors and acceptors in its crystal structure, TTF donors aggregate with long alkyl groups by CH/pi and/or van der Waals interactions in a couple of TTF-heptylviologen complexes.     

The tuneable complexation of gold nanoparticles

Mixed monolayer protected gold nanoparticles have been fabricated incorporating 1,5-dialkyloxynaphthalene moieties that are capable of forming complexes with the tetracationic cyclophane cyclobis(paraquat-p-phenylene); electrochemical reduction of the cyclophane or the addition of tetrathiafulvalene results in disassembly of the complexes.     

Synthesis and characterization of a new family of spin bearing TTF ligands

The syntheses and characterization of two new tetrathiafulvalene (TTF) derivatives bearing pyridine-based substituents and 1,5'-dimethyl-6-oxoverdazyl radicals are described. The TTF-pyridine and bipyridine aldehydes were prepared via a palladium-catalyzed cross-coupling reaction between mono(tributylstannyl)tetrathiafulvalene (3) and the appropriate formylpyridyl halides (4). The radical precursors, the corresponding 1,2,4,5-tetrazanes, were prepared by condensation of the bis(1-methylhydrazide) of carbonic acid with the TTF bearing pyridyl aldehyde. Oxidation of tetrazanes 8 and 9 with 1,4-benzoquinone afforded the donor radicals 1 and 2 as 1:1 complexes with hydroquinone. Both complexes are stable in the solid state and their electronic properties have been characterized by EPR, cyclic voltammetry, and UV/vis spectroscopy. The TTF core of both compounds was oxidized both chemically and electrochemically to afford the corresponding cation diradical species. The electronic properties of both donor radicals have been probed by cyclic voltammetry, UV-vis spectroscopy, and preliminary EPR measurements.     

Synthesis and properties of novel unsymmetrical donor molecules containing p-acetoxy- or p-hydroxyphenyl units

We report the synthesis and properties of eight new tetrathiafulvalene (TTF) derivatives containing two different functionalities, prepared with the aim of obtaining stable organic materials. The four acetoxyphenyl- and four hydroxyphenyl TTFs were synthesized via Wittig-type condensations. The electrochemical properties of these redox-active molecules were studied by cyclic voltammetry. Charge transfer complexes with tetracyanoquinodimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials. The UV-VIS and IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.     

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 =...     

Steric conditions for donor–acceptor interactions in C60 complexes with planar organic donors

Charge transfer complexes of fullerene C₆₀ with planar donors of tetrathiafulvalene, dithiadiazafulvalene and pyranylidene family were investigated by IR- and UV-VIS-NIR spectroscopy. The analysis of IR and X-ray data shows that the charge transfer complexes of fullerene with the planar donors are involved in polarization interactions of van der Waals type. Charge transfer is very weak in these compounds and is hindered by unfavourable steric factors. As a result, the CT rate does not correlate with the ionization potential of the donor; the charge transfer absorption bands are very weak too.