【作者】 丁一；

【导师】 宁桂玲； 仲剑初；

【作者基本信息】 大连理工大学 ， 化学工艺， 2009， 博士

【摘要】 四硫富瓦烯（TTF,tetrathiafulvalene）是一种优良的电子给体,当与适当的受体结合时,它们较易被氧化并形成稳定的自由基阳离子,并生成具有导电性甚至超导性能的分子导体。因此,自1973年第一个具有超导性能的基于四硫富瓦烯的电荷转移复合物TCNQ-TTF诞生以来,TTF及其衍生物成为近三十多年来人们所热衷的研究热点,它是一些导电材料、超导材料和半导体材料的重要组成部分。至今,仍不断有新的分子导体被报道。另一方面,自从结构化学相关理论逐渐成熟,X-射线单晶衍射技术的完善和发展对人们研究化合物的分子结构起到了重大的推进作用。科学家对TTF及其衍生物的研究已不局限于单纯合成具有较高导电性能的分子导体,它们更被广泛地应用于合成具有一定功能特性的功能配位化合物（光、电、磁等）,而从结构上对该类化合物进行设计和改良,也成为推进该领域发展的重要途径之一。近年来,科学家们在TTF类分子导体方面的研究倾向于设计开发具有更加广泛的π共轭体系的稠合的TTF衍生物和金属配位化合物,但是,一些具有较小分子尺寸的TTF衍生物却被忽视。本论文中,我们不仅按照常规思路设计、合成了具有不对称取代基的单TTF骨架、稠合TTF骨架（TTP,tetrathiapentalene,四硫并戊烯）类化合物,更对一些具有较小分子尺寸的dmit类化合物及其金属配位化合物进行了深入的研究,从结构上考察了金属-dmit（2-硫酮-1,3-二硫代环戊烯-4,5-二硫基）衍生物的配位组装规律。研究结果如下:1.采用传统的Wittig偶合反应,以亚磷酸三甲酯和亚磷酸三乙酯作为偶联剂,二硫化碳为起始原料,设计、合成了13种单骨架和双骨架（双稠合）TTF衍生物:2,3-二氰乙硫基-6,7-烷硫基四硫富瓦烯、2,3,6,7-四氰乙硫基四硫富瓦烯及2-（4’,5’-二烷硫基-1’,3’-二硫代环戊烯-2’-叉）-5-（4’,5’-二氰乙硫基-1’,3’-二硫代环戊烯-2’-叉）-1,3,4,6-四硫并环戊烯。其中,烷基取代基分别为:甲基、乙基、丙基、丁基、戊基和己基。通过表征证实了产物结构的正确性,也验证了合成路线的可行性。采用循环伏安法对这13种化合物的电化学性质进行了分析,采用两极法对6种双稠合TTF类产物进行了导电性能测定,从结构角度讨论、总结了不同烷基取代基对化合物导电性能的影响。对于单TTF骨架类产物来说,一侧烷基取代基和另一侧柔性氰乙硫基的成功引入为我们后续合成具有新颖空间结构的金属-TTF配位化合物提供了合适的有机配体。2.利用前期合成的2,3,6,7-四氰乙硫基取代四硫富瓦烯（tces-TTF）和2,3-二氰乙硫基-6,7-二乙硫基四硫富瓦烯（CE-TTF）及2种Ag（Ⅰ）金属盐（AgCF₃SO₃和AgSbF₆）,合成了几种具有独特的螺旋结构的Ag（Ⅰ）-TTF金属配位聚合物[Ag₄（tces-TTF）₂（CF₃SO₃）₂]（CF₃SO₃）₂和[Ag（CE-TTF）（CF₃SO₃）]·acetone,并成功地获得其单晶。通过X-射线单晶衍射分析表征的结果,对产物结构进行了细致的讨论,发现氰乙硫基取代基是螺旋结构形成的主要因素,这与我们的设计思路一致。此外,还对几种Ag（Ⅰ）-TTF金属配位化合物的导电性进行了测试,考察了化合物结构中存在的S…S相互作用,探讨了该类分子内部结构对化合物导电性能的影响规律。3.以几种TTF衍生物合成过程的中间体R₂dmit为配体,与AgCF₃SO₃、AgSbF₆等银盐进行反应,合成出几种具有特殊结构的金属配位化合物:具有新颖的多螺旋结构的[Ag₂（bmdt）₂]（SbF₆）₂·acetone和具有三维开放网络结构的[Ag₄（bcdt）₄]（CF₃SO₃）₂·（CF₃SO₃）₂·acetone,并获得其单晶。通过X-射线单晶衍射对两种化合物的结构进行了分析,对前者特殊的螺旋结构的形成机制做出了初步假设;通过对后者配体的单晶结构与其配合物进行结构对照,对R₂dmit配体的组装模式进行了初步探讨,对Ag（Ⅰ）在该类化合物中的配位模式进行了分析和总结。采用两极法对化合物电导率进行了测定,讨论了S…S相互作用的强弱和维度这两个方面对化合物导电性能的影响。4.采用R₂dmit与AgClO₄反应,得到了相应产物及其单晶。通过X-射线单晶衍射实验对其结构进行了分析,结合前面合成的几种Ag（Ⅰ）-R₂dmit化合物的晶体结构,全面考察了Ag（Ⅰ）及R₂dmit配体的组装特性,提出了Ag_n（R₂dmit）X_n·Y体系（其中,n=1,2,4;R=甲基,乙基,氰乙硫基;X=CF₃SO₃^-,SbF₆^-,ClO₄^-;Y=溶剂分子）,并对该体系中金属与配体间的组装规律进行了初步探讨,给出了相应的结论。更多还原

【Abstract】 TTF（tetrathiafulvalene） is an excellent donor,when coulped with proper acceptor,they are easily oxidized to stable radical cations,which lead to molecular conductors with conductive or even super-conductive properties.Since 1973,the first CT（charge transfer） complex TCNQ-TTF was synthesized,TTF and its derivatives have been studied by scientists for more than three decades,and they are important components of some conductive, super-conductive or semi-conductive materials.Nowadays,new molucular conductors based on TTF are frequently reported.On the other hand,when the theories of Structure Chemistry imporved gradually,the development of X-ray single crystal diffraction technologies plays an important role for people studying molecular structures.The design and synthesis of TTF derivatives are no longer limited in the field of preparing high-conductive molecular conductors,they are widely used to obtain functional coordinate complexes with special functions,such as optical, electrical and magnetical.So studying the effects of the structure to their properties are one of the best methods to design new functional compound.Recently,bis-and tris-TTF derivatives with wide a-conjugated system has been synthesized and studied,however,some small-sized TTF derivatives which also inheritid properties of TTF molecules were less studied.In this work,we not only synthesized some unsymmetric TTF/TTP（tetrathiapentalene） compounds,but also used some dmit ligands with small size to design and synthesis some Ag（Ⅰ） coordinated compounds,the structures and properties are also analyzed and discussed, by which we draw our conclusion on the assembly rules of these R₂dmit ligands.1.By traditional Wittig couple reaction,13 TTF derivatives are designd and synthesized from P（OMe）₃,P（OEt）₃ and CS₂:2,3-bis（cyanoethylsulfanyl）-6,7-bis（R-sulfanyl）-TTF, 2,3,6,7-tetra（cyanoethylsulfanyl）-TTF and[2,3-bis（cyanoethylsulfanyl）-6’,7’-bis（R）-TTP]（R= Me,Et,...Hex）.The structures of products are characterized and our synthesis route is proved to be right.Cyclic voltammograms are obtained to analyze the electrical properties of the products,and the conductivites are tested by traditional twoprobe method.For the bis-TTF products,similar structure was reported before,so the effects of structures to their conductive behavior are comparely discussed.Additionally, the flexible cyanoethylsulfanyl group is successfully induced to the TTF system,which will be fully dicussed in our following studies.2.Tces-TTF and CE-TTF were used,together with some Ag（Ⅰ） salts,AgCF₃SO₃ and AgSbF₆,to synthesize two Ag（Ⅰ）-TTF coordinate compounds with novel helical motifs. As expected,we obtained the product[Ag₄（tces-TTF）₂（CF₃SO₃）₂]（CF₃SO₃）₂ and [Ag（CE-TTF）（CF₃SO₃）].acetone,the single crystals are analyzed by X-Ray diffration, structures and helices in the molecular structure are discussed,S…S contacts are found which result in the conductive property of the products.3.Some R₂dmit ligands are used to synthesize Ag（Ⅰ）-TTF coordinate compounds with AgCF₃SO₃、AgSbF₆·[Ag₂（bmdt）₂]（SbF₆）2·acetone with novel multi-helical structure and [Ag₄（bcdt）₄]（CF₃SO₃）₂·（CF₃SO₃）₂·acetone with 3D open network are obtained.The assembly rules of R₂dmit ligands in Ag（Ⅰ） surroundings and the coordination geometry of Ag（Ⅰ） ions are discussed.Electrical properties are also studied.4.R₂dmit and AgClO₄ salt are used to synthesize Ag-dmit products.Together with some structures we obtained before,the Ag（Ⅰ） and R₂dmit coordinate mode are fully compared and studied,as a conclusion,a new M-TTF system,Ag_n（R₂dmit）X_n·Y is illustrated here （n=1,2,4;R=Me,Et,Cyanoethylsulfanyl;X=CF₃SO₃^-,SbF₆^-,ClO₄^-;Y= solvent molecules）,the assembly rules are analyzed and discussed.更多还原