Crystal Structures And Properties Of The Coordination Complexes With Pyridyl-TTF Ligand

Tetrathiafulvalene(TTF) and its derivatives have stimulated great interest for a long time due to their unique donor and redox properties. They have been used in many fields such as supramolecularchemistry, photoelectric switch, biological sensors, electrode material and so on. Polypyridyl metal complexes can be used as molecule-level wires, molecular sensing materials and so on, therefore, they have also been widely studied. The TTF derivatives substituted by pyridyl can coordinate to a metallic centre to form a complex with electronic properties. When TTF and pyridyl are connected directly, it will increase the coupling between organic π electrons(TTF and pyridyl), organic ligands and d electrons of metals. Therefore, complexes containing these ligands can be used as bricks in the field of potential molecular materials. There are few reports about double-pyridyl group directly connecting with the TTF compound. On the other hand, in comparison with the transition metal complexes, TTF- main group metal coordination polymers have not been thoroughly studied so far. In this thesis, our main work is to introduce the main group metal Pb2+ to the TTF system to give the Pb-TTF coordination polymers. In addition,their crystal structures and chemical properties have also been studied. The major contents are as follows:1、In introduction, the properties and research progress of TTF derivatives are reviewed briefly. Recent researches on TTF derivatives substituted by pyridyl are summarized. Finally, the significance and the main contents of the thesis are introduced.2、Two py-TTF-py-lead complexes, one cadmium complex and one cobalt complex with the coligand anthracene acid formulated as [Pb(AC)2(py-TTF-py)2](1)(0-D), {[Pb(AC)2(py-TTF-py)0.5]?CH3CN}n(2)(2-D), [Cd(AC)2(py-TTF-py)2]n(3)(1-D), [Co(AC)2(py-TTF-py)2]n(4)(0-D). The structures of these complexes were characterized by single crystal X-ray analysis. Besides, spectroscopic and electrochemical properties of these complexes have been studied, which indicate that charge transfer occurs in these complexes and they are electrochemically active materials. The fluorescence properties have also been discussed. We find that metal coordination centers play an important role in improving the fluorescence response property, which laid the foundation for the synthesis new electrochemically active materials.3、Three py-TTF-py-lead complexes and one cadmium complex with the coligand benzoic acid formulated as [Pb(bza)3(py-TTF-py)0.5]n(5),[Pb(bza)2(py-TTF-py)0.5]n(6),[Pb(bza)(py-TTF-py)(NO3)]n(7), and [Cd(bza)2(py-TTF-py)]n(8) are prepared. The structures of these complexes were characterized by single crystal X-ray analysis. In addition, spectroscopic and electrochemical properties of these complexes have been studied. Crystal structure analysis show that compounds 5 and 6 are two-dimensional(2-D) coordination polymers, and compounds 7 and 8 are one-dimensional(1-D) chain coordination polymers. The electrochemical results show that these four complexes are electrochemically active materials.