Synthesis, Structures And Properties Of Functional Coordination Complexes Derived From Tetrathiafulvalene (TTF) And Ag(â… )

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(â… ) 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(â… ) salts,AgCF₃SO₃ and AgSbF₆,to synthesize two Ag(â… )-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(â… )-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(â… ) surroundings and the coordination geometry of Ag(â… ) 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(â… ) 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.