Synthesis And Properties Of TTF-Caboxylate Modified Titanium-Oxo-Clusters

Tetrathiafulvalene and its derivatives have attractive electron-donating and reversible redox properties. The design and synthesis of TTF derivatives functionalized by various coordination groups and the corresponding metal complexes have been extensively studied. These TTF–metal complexes offer a novel perspective on multifunctional properties, for example, as photoactive molecular materials. TTF derivatives have been adsorbed onto the Ti O fims of photoactive systems and applied in dye-sensitized solar cells. However, TOCs grafted with the TTF moiety have not yet been explored. The first compound successfully combining TOCs with a TTF ligand was prepared and characterized by single-crystal analysis. The major studies of this work are as follows:In introduction, the properties and important achievements of TTF derivatives are reviewed briefly. The research progresses in crystal structures and recent development of Ti-O clusters are described.In chapter 2, [Ti6O3(O i Pr)14(L)2]?0.5H2O(Ti O–L)(HOi Pr =isopropanol, L=dimethylthio-TTF dicarboxylate) was prepared under solvothermal condition, in which TTF ligand as the functionalized compound is successfully combined with TOC. The molecular structure was characterized by single-crystal analysis. The band structure of the cluster is modified by the coordination of the TTF ligand and the absorption of the material is improved. Fundamental studies of the photocurrent response of the Ti O–TTF materials were carried out.The unique application of TTF and TOCs in both theoretical and practical aspects need to be further explored.In chapter 3, We studied the self-catalyzed and oxidized properties of the crystal Ti O–L. The red crystal of the Ti O–L cluster turned black in an oxygen atmosphereand this black ‘crystal’ was composed of regularly arranged board-like micro-plates. The good exfoliation properties of the material arise from the easy oxidation of the TTF group and the catalytic properties of the Ti O cluster. Combined with Ti O–L, Ti O–L(+) has an more effective photocurrent response. This is the cooperative effect of L(+) and Ti O, both of which have effective photocurrent response.In chapter 4, TTA was successfully combined with TOC and characterized by single-crystal analysis. The work lays the foundation for future study.