Syntheses And Characterization For TTF Based Dual-functional Materials

Molecular magnetic materials were newly developed in past decades. As highly ordered molecular systems, they are superior to traditional magnetic materials in many fields, such as low density, solubility, transport, tuning properties, flexibility. Organic conductor and organic superconductor have attracted much interest in recent years. It is known that some organic materials can change into conductor or superconductor by doping with organic or inorganic ions. In early 60th, Little and McConnell put forward the theory of room superconductor and ferromagnet, respectively. It encourages scientists to do their best to realize these systems. The variety of organic and coordination polymers provide the possibility to design and syntheses of complexes with conductive and magnetic character. It is very important for theory and application that interrelated physical character is exhibited within one component material. Introducing paramagnetic ions into organic conductor system is still a popular method in design and synthesis of conductive and magnetic materials. There are generally two effective methods to introduce inorganic ions. Firstly, donors and paramagnetic ions are self-assembly by interactions between molecules. There will be strong interactions between organic molecules and inorganic sublattices. Secondly, donors connect paramagnetic ions directly through chemical bond. Conductivity and magnetism then can be realized within one complex. In order to design dual-functional materials, pyridine substituted tetrathiafulvalene (Py-TTF) has been synthesized, and then, its complex containing paramagnetic ion was prepared. The structure of prepared complex was confirmed by X-ray measurement. The electrochemistry character for Py-TTF was investigated. The prepared complex Ni(acac)₂(Py-TTF)₂ can be regarded as an example of the second method referred above. The basic starting materials for target complex such as TTF and M(acac)2 (M=Cu²⁺, Ni²⁺, Mn²⁺) were synthesized as well. Tetra(methylsulfanyl)tetrathiafulvalene (TTMTTF) was synthesized, and paramagnetic ions were introduced using electrochemistry. In this experiment, we also synthesized basic materials TTMTTF and inorganic salts firstly. For (Me₄N)₃FeO_x3, Me₄NFeCl₄, and TTMTTF systems respectively (CH₂Cl₂ as solvent), the same product (TTMTTF)FeCl₄ was obtained. Therefore, (Me₄N)₃FeO_x3 and CH₂Cl₂ decomposed, they offered Fe³⁺, Cl^-, respectively. In another experiment, (TTMTTF)C₂O₄Cl was obtained in the system of (Me₄N)₃FeO_x3, TTMTTF and CH₂Cl₂. This is another evidence that the decomposition of (Me₄N)₃FeO_x3 and CH₂Cl₂. Hence, CH₂Cl₂ is not a suitable solvent in these systems. The magnetic data of (TTMTTF) FeCl₄ indicated that there are strong antiferromagnetic interactions between Fe³⁺ ions, although the shortest distance is 0.733 nm. Furthermore, we have studied some complexes synthesized by hydrothermal syntheses.