Synthesis And Properties Of Novel Tetrathiafulvalenes(TTFs) Based On Pyridine

Due to the unique structures and properties of Dafo（4, 5-Diazafluoren-9-one）-based TTF（Tetrathiafulvalene） compounds, the Dafo based TTF derivatives containing pyridine have been of wide concern. In this thesis, based on functional molecular recognition and assembly principles, 6 novel TTF derivatives containing pyridine were synthesized, and characterized by ¹H NMR, ¹³ C NMR, FT-IR and MS-ESI spectroscopy. And interactions of TTF derivatives with metal ions were studied by cyclic voltammetry（CV） and UV-Vis. This thesis mainly includes the following aspects:1. The research development of TTF and TTF derivatives with pyridine was reviewed briefly.The structures 、 properties and application of TTF derivatives containing pyridine and Dafo in coordination chemistry and functional materials were briefly reviewed.2. The thione, ketone and TTF derivatives containing pyridine by sulfur bridge bond were synthesized, and the oxidation potentials of TTF derivatives by CV and crystal structures were studied. Combined with theoretical calculations, we analyzed the influence of pyridine in different positions on the electrochemical behavior of TTF.2-Iodine pyridine, 3-iodine pyridine, 4-iodine pyridine and zinc salt used as starting materials, 4,5-bis（pyridin-2-ylthio）-1,3-dithiole-2-thione（I）, 4,5 –bis（pyridin-3-ylthio）-1,3-dithiole-2-thione（II） and 4,5-bis（pyridin-4-ylthio）-1,3-dithiole-2-thione（III） were obtained via C-S coupling reaction in the presence of Cu（I） catalysis. Then 4,5-bis（pyridin-2-ylthio）-1,3-dithiole-2-one（Ia）,4,5-bis（pyridine-2-ylthio）-1,3- dithiole-2-one（IIa） and 4,5-bis（pyridin-2-ylthio）-1,3-dithiole-2-one（IIIa） were synthesized by oxidation of thiones compounds（I, II and III） with mercury acetate. Finally, 2,3,6,7-tetrakis（pyridine-2-ylthio）tetrathiafulvalene（Ib）, 2,3,6,7-tetrakis（pyridine-3-ylthio）tetrathiafulvalene（IIb） and ,3,6,7-tetrakis（pyridine-4-ylthio） tetrathiafulvalene（IIIb） were achieved through the self coupling of compounds（Ia, IIa and IIIa）. Moreover, compounds（III, IIIa, IIIb）were characterized by ^H NMR, ¹³ C NMR, FT-IR and ESI-MS. And the structures of the compounds（II, IIb and IIIb） were determined by single crystal X-ray diffraction.The oxidation potentials of compounds Ib, IIb and IIIb were studied by CV, which presented a reversible two-electron redox process. The calculations at the density functional theory B3LYP/6-31G（g）level,available in Gaussian 09, were carried out and the energies of frontier orbitals in Ib, IIb and IIIb were obtained.3. The Dafo based TTF derivatives were synthesized, and the interactions between the compounds and ions were studied by CV and UV-vis spectroscopy.Through the cross coupling reactions of compounds（ I, II and III） with Dafo,4,5-diaza-9-[4,5-bis（ pyridin-2-ylthio）-1,3-dithiol-2-ylidene]-fluorene（Ic）,4,5-diaza-9-[4,5-bis（ pyridin-3-ylthio）-1,3-dithiol-2-ylidene]-fluorene（IIc） and4,5-diaza-9-[4,5-bis（ pyridin-4-ylthio）-1,3-dithiol-2-ylidene]-fluorene（IIIc） were obtained. And compounds（Ic, IIc and IIIc） were characterized by 1H-NMR,13C-NMR and ESI-MS. Besides, the structures of the compounds（IIc and IIIc） were determined by single crystal X-ray diffraction. The electrochemical behaviors of compounds（Ic, IIc and IIIc） were studied by CV. And the maximum absorption wavelength was found to shift to long wavelength when Cu²⁺、Cd²⁺、 Hg²⁺、 Zn²⁺、Fe²⁺ 、Ag⁺ and Al³⁺ were added by UV-Vis spectroscopy.