【作者】 陈霞；

【导师】 方奇；

【作者基本信息】 山东大学 ， 材料学， 2008， 硕士

【摘要】 二十世纪70年代初合成的含4个硫原子的多硫电子给体TTF（Tetrathiafulvalene,C₆S₄H₄）型电子给体是分子导体领域中著名的电子给体。10年后TTF型电子给体的硫原子数扩充到8,例如分子超导体中首屈一指的电子给体BEDT-TTF(Bis（4,5-ethylenedithio）tetrathiafulvalene,C₁₀S₈H₈)。近年来出现的以TTP（tetrathiapentalene,四硫并环戊烯）为结构特征的多硫电子给体是TTF体系的一个新的扩展。体现在其硫原子数目进一步增加,分子平面和共轭性更加增强。合成的难度也进一步加大,例如流程骤增,产物复杂,溶解性骤减。本论文的研究目标是合成含12个硫原子或16个硫原子的新型多硫电子给体,为发展新一代分子导体和半导体开辟道路。我们从含2个硫原子的CS₂出发,逐步扩大分子的尺度和π共轭体系,合成了许多前体化合物。在探索反应条件方面（例如偶合反应的探索）,进行了大量实验工作,完成了合成BVDT-TTP（含12个硫原子）的预定目标,并进一步合成了含16个硫原子的BVDT-TTPY。1.首次合成含12个硫原子的多硫电子给体BVDT-TTP:2,5-bis（4,5-vinylenedithio-1,3-dithio-2-ylidene）-1,3,4,6-tetrathiapentalene2,5-二（4,5-亚乙烯基硫-1,3-二硫-2-亚基）-1,3,4,6-四硫并环戊烯并首次测定了BVDT-TTP的分子结构和晶体结构。长度为18.6 nm的BVDT-TTP分子基本为平面构型,两端的亚乙烯基分别向上向下翘离平面,其余22个原子共平面。分子良好的平面共轭性,保证电子在分子内的充分离域。晶体中所有分子平行堆积,相邻上下分子的面间距为0.3578 nm,具有较强的分子间的π-π相互作用,有利于电子在分子间的迁移。2.首次合成含16个硫原子的多硫电子给体BVDT-TTPY:2,2’-bis[4,5-vinylenedithio-（1,3-dithio-2-yidene）-1,3,4,6-tetrathiapentaleneylidene]2,2’-二[（4,5-亚乙烯基硫-1,3-二硫-2-亚基）-1,3,4,6-四硫并环戊烯]3.首次测定了VDTO-TTP的分子结构和晶体结构,它是上述BVDT-TTP和BVDT-TTPY的直接前体。更多还原

【Abstract】 In the early 1970s,the multi-sulfur electronic donor TTF（Tetrathia-fulvalene, C₆S₄H₄）came into being as the most famous electronic donor in the area of molecular conductors.Ten years later,the number of sulfur atom in the TTFs electronic donor had been added to eight,for example,the best electronic donor in the area of molecular superconductors,the BEDT-TTF(Bis（4,5-ethylenedithio）tetrathiafulvalene,C₁₀S₈H₈).Recently,the multi-sulfur electronic donors with TTP（tetrathiapentalene）moity are a new enlargement of the TTFs.Its sulfurs number had been farther expanded,the molecular planarity and theπ-conjugation been much improved.At the same time,the synthesis became more and more difficult,for example,the steps had to be increased and the solubility of the resultant compounds reduced sharply.The main goal of this thesis is to synthesize the new multi-sulfur electronic donor with 12 or 16 sulfur atoms,to blaze a way in the development of new molecular conductors and molecular superconductors.We started from the CS₂ with 2 sulfurs,and enlarged the molecular dimension step by step,harvested many intermediae compounds, carried through large mumber of experiments to explore the reaction conditions（for example,the conditions of coupling reaction）,and finally we successfully synthezied our target electronic donor BVDT-TTP with 12 sulfur atoms and further more the BVDT-TTPY with 16 sulfur atoms.1.Firstly,we synthesized the electronic donor BVDT-TTP with 12 sulfur atoms.2,5-bis（4,5-vinylenedithio-1,3-dithio-2-ylidene）-1,3,4,6-tetrathiapentalene we firstly determined the molecular strcture and crystal structure of BVDT-TTP.The BVDT-TTP molecular with the length of 18.6 nm is almost planar,except that the vinylenes on the two ends tilt from the plane.The other 22 atoms are in the same plane. The planarity andπ-conjugation make theπ-electrons delocalized on whole molecules. All of molucules in the crystal accumulate are parallely packed,the distance between two molucules is 0.3578 nm.There is quite strongπ-πinteraction between neighbouring molucules,it is good for electrons to move. 2.We firstly synthesized the electronic donor BVDT-TTPY with 16 sulfur atoms.2,2’-bis[4,5-vinylenedithio-（1,3-dithio-2-ylidene）-1,3,4,6-tetrathiapentaleneylidene]3.We firstly determined the molecular strcture and crystal structure of VDTO-TTP,the direct precursor of BVDT-TTP and BVDT-TTPY.更多还原