【作者】 安彩霞；

【导师】 尹炳柱；

【作者基本信息】 延边大学 ， 有机化学， 2006， 硕士

【摘要】 四硫富瓦烯（TTF）能以三种不同且稳定的氧化还原态形式存在，因此在材料化学和超分子化学方面被广泛研究。例如：作为L-B膜沉积物、非线性光学材料、有机铁磁体、阳离子传感器、分子开关、稠合冠醚作为配体等。近十年来，利用TTF或者TTF衍生物作为构筑骨架合成大分子、环盘烷和笼状分子化合物已经成为TTF化学领域中的研究热点之一。 首先，用2-氰乙硫基-3，6，7-三取代的四硫富瓦烯和三（碘乙基）胺或a，a′，a″-三溴均三甲苯反应，高产率合成了带有三个四硫富瓦烯结构单元三角型电子给体化合物，并用¹H NMR，¹³C NMR和元素分析进行了结构表征。紫外光谱和核磁共振测定实验结果表明，在溶液中目标化合物对C₆₀不显示识别作用。化合物4c由于空间因素的作用显示出独特的氧化还原过程。 其次，成功地合成出了六个单吡咯并TTF的衍生物，即四个MPTTF-p-A型化合物和两个MPTTF-p-D’化合物，并用¹H NMR，（13）C NMR，IR，MALDI-TOF-MS进行了结构表征。从目标化合物20a-b的UV吸收可以观察到，分子内的电荷转移的发生。17a-b and 20a-b四种化合物具有共轭的推-拉结构，故有望具有良好的NLO性能。最后，尝试合成含有四个TTF结构单元的杯[4]吡咯，但未得到目标化合物。更多还原

【Abstract】 Tetrathiafulvalene（TTF） is able to exist in three different stable redox states(TTF, ITF⁺ , and TTF²⁺ ). For this reason TTF derivatives have found widespread use in novel materials chemistry and supramolecular chemistry, for example, crown-annelated ligands, Langmuir- Blodgett film deposition, cation sensors, nonlinear optical materials, supramolecular switches, organic ferromagnets, and so on. During the last decades, TTF and TTF derivatives have been utilized as building blocks in macrocycles, cyclophanes and cage structures, which is one of the most extensively studied fields.In this paper, first, we synthesized four the tripod-type compounds with three TTF unit as electronic donor in good yields by Cyanothylthio-3,6,7-trisubstituted TTF reacting with tri（2-iodoethyl）amine or tribromomethylbenzene. Their structures were confirmed by ¹H NMR, ¹³C NMR and elemental analysis and their electrochemical behaviors were investigated by meanes of cyclic voltammetry. According to UV and ¹H NMR, target compounds didn’t include C₆₀ in solution. Compound 4c exhibited the unique redox processes on account of its p-electron rigid structure.Secondly, we successfully obtained four monopyrrolo-tetrathiafulvalene-p-A （MPTTF-p-A） type compounds and two monopyrrolo-tetrathiafulvalene-p-D’ （MPTTF-p-D’） type compounds from formylated precursor. The target compounds were characterized by ¹H NMR, ¹³C NMR, MALDI-TOF-MS. From UV-Vis spectra of target compounds 20a-b, the intramolecular charge-transfer （CT） absorption bands are observed. Compounds 17a-b and 20a-b likely have good third-order NLO properties due to having conjugated pull-push structural unit. Finally, the synthesis of更多还原