The Design, Synthesis Of Terpyridine Derivatives Based On Tetraphenylsilanes And Properties Of Metal Complexes

Zinc is involved in the composition of 200 kinds of human enzymes, especially directly in the synthesis of protein and nucleic acid, the cellular differentiation and proliferation, and many important metabolic reactions. Therefore,zinc was praised as “ the flower of life”. On the contrary, cadmium, an element of the same group, is of environmental pollutant rather than an essential element.Traditionally, overdosing on cadmium, which is classified into carcinogen,may cause the human body poisoned. Therefore, it is of great significance to synthesis the organic materials which is responding specially to d10 transition-metal ions.We found tetraphenylsilane compounds possessed good thermal stability as host materials. And for the sp3 hybridization of Si atom, tetraphenylsilane presented a tetrahedron configuration. This structure could effectively interrupt the conjugation length, making the charge transferring from donor to acceptor forbidden.Simultaneously, this configuration also prevented molecules packing too closely, and it is also a great help to form a certain configuration of supramolecular complexes. In a word, tetraphenylsilane was good for constructing deep-blue, near-ultraviolet or ultraviolet-emitting organic materials. In addition, 2,2’:6’,2”-terpyridine(tpy) was an excellent organic ligand for it can act as donor and acceptor at the same time. As a tridentate ligand, when it chelated with metal ion, they could form a six-coordinated metal complex, and the octahedron structure was most stable for possessing the lowest energy.In Chapter 3, we mainly discuss the synthesis and optical properties of get near ultraviolet and deep-blue light material in different ways to link the tetraphenylsilane and terpyridine. To the best of our knowledge, three kinds of materials synthesis has not been reported so far. So, we will firstly describe the stepwise chemical reaction method of three terpyridine derivatives based on tetraphenylsilanes. Then we will discuss the electronic cloud distribution of HOMO and LUMO of the synthesized materials, as well as the nature of protonated terpyridine. The emission peak of EL spectrum of ultraviolet light-emitting material TSI-TTPY and deep-blue light material TSI-OCTPY was 361 nm and 423 nm, respectively. The emission peak of EL spectrum of two materials happen the different degrees of red-shift with different intensity of Lewis acid, both ?λem have 190 nm and 180 nm, respectively.In Chapter 4, we mainly discuss the study of optical properties of TSI-TTPY and TSI-OCTPY with different transition metal ion, especially two ligand have potent specific with Zn2+ and Cd2+. To achieve a better performance of response to transition metel ion, we tested change of EL spectrum of two ligand with Zn2+in different aqueous-organic solvents, eventually selects THF and acetonitrile as solvent to use when spectroscopic tests. In the presence of Zn2+, the emission peak of EL spectrum of TSI-TTPY and TSI-OCTPY shows red-shift, ?λem have 60 nm and87 nm, respectively, the former being “ turn-on ” change, while the latter being change of emissive color. Having taken test and quantitative analysis,coordinated mode between terpyridine and Zn2+ adopt octahedron in two compound.Besides, TSI-TTPY display an obvious fuchsia color upon selectively binding with Fe2+, allowing a rapid identification of Fe2+ in the THF media by naked eyes. Because TSI-TTPY has two coordination sites, it with Zn2+ by self-assembly to form the lamellar structure and balloon-like sac under different condition.