在甲醇钠的作用下,2分子的2,3-二(2''-氰乙基硫基)-6,7-二丁硫基四硫富瓦与2分子的2,6-二(氯甲基)吡啶反应生成四硫富瓦烯-吡啶结构单元的新型环蕃(3)。在离子液中测定了新型环蕃3的电化学性质,并研究了其对金属离子识别的性能。实验结果表明:在离子液中,环蕃中四硫富瓦烯单元更加容易被氧化或还原,而且其紫外吸收也显著增强;同时发现Pb2+对这种新型环蕃化合物的紫外吸收和氧化还原电位的影响最为明显,其对Pb2+有一定的选择性识别功能,Cu2+能够破坏TTF结构单元。

With the effect of sodium methoxide,two molecular of 2,3-bis(2′-cyanoethylthio)-6,7-bis(buthylthio)-tetrathiafulvalene reacted with two molecular of 2,6-bis( chloromomethyl) pyridine to afford a novel tetrathiafulvalene-pyridine structure unit-cyclo-phane(3). Electrochemical properties of cyclophane 3 were determined and its recognition for metal ions were also investigated. The experiment results showed that tetrathiafulvalene units of the novel cyclophane were more easily to be oxidized or reduced in ionic liquid. The UV-vis absorption spectrum and redox property of the TTF cyclophane showed remarkable sensing and coordinating properties to Pb2+,so the TTF cyclophane could selectively recognize Pb2+ by the unique properties. The tetrathiafulvalene structure units was destroyed by Cu2+.

基于密度泛函理论结合跳跃模型和能带理论研究了氟、氯、氰基和N原子的引入对四硫富瓦烯(TTF)衍生物载流子传输性质的影响.计算结果表明,嵌N修饰会降低分子重组能,特别是当N原子靠近TTF主体环时作用更明显.与引入卤素修饰相比,引入氰基修饰的分子具有更小的电子和空穴重组能及更低的前线分子轨道(FMO)能级.同时迁移率的计算结果显示,分子6具有1.15 cm2·V-1·s-1的高电子迁移率,考虑其较低的LUMO能级,推测其有望成为潜在的优异电子传输材料,而相似的电子和空穴迁移率使分子2有望成为潜在的双极性传输材料.同时还考察了S和N原子之间的弱相互作用,当S或N原子对分子HOMO(或LUMO)有贡献时,其相应的空穴(或电子)传输能力会有所提高.

The density functional theory and hopping model with band theory were employed to calculate the charge carrier transport properties of six planar polycyclic aromatic hydrocarbon fused tetrathiafulvalene(TTF) derivatives. The effects of halogen, cyan substitutions and nitrogen were investigated in details. It was con-firmed that the introduction of N-atoms reduced the molecular reorganization energy especially when the N-atoms were modified next to the TTF core. Comparing to the halogen the cyan group modified molecules be-have lower reorganization energy and lower frontier energy level. The calculated electron drift mobility of mole-cule 6 is 1. 15 cm2 ·V-1 ·s-1 . More over the molecule maintains the lowest LUMO energy level, implying that the molecule may exhibit good electron transport property. The calculated electron dirft mobility(0. 37 cm2 ·V-1 ·s-1 ) of molecule 2 is very close to hole dirft mobility(0. 34 cm2 ·V-1 ·s-1 ), indicating molecule 2 is suitable for bi