Synthesis, Crystal Structures And Spectroscopic Study On Cu(Ⅰ) Complexes Of 4'-pyridyl-2,2': 6',2"-terpyridine

We have focused on the design and the synthesis of a series of functionalized terpyridines and their CuX (X=I, CN^-, SCN^-) complexes by hydrothermal or solventthermal in this work. By alternating the oxidations states of the metal centers, increasing stoichiometric metal/ligand ratio and introducing a second ligand, the compounds, as expected, were successfully developed from simple mononuclear to multinuclear and polymers. The synthesis of these compounds may provide a new approach for the construction of coordination polymers of 4'-pyridyl terpyridine. The thesis is divided into three chapters.In chapter 1, the study background of this work is concisely introduced with the emphasis on the synthesis of 4'-functionallized terpyridine and the current survey of terpyridine coordination compounds. The studies on quarter, quinque and sexipyridine were also mentioned. Finally, the meaning of this work was also narrated.In chapter 2, seven novel complexes of ligand (4'-(2-pyridyl)-2,2':6',2"-terpyridine (L1), 4'-(3-pyridyl)-2,2':6',2"-terpyridine (L2)) and CuI were prepared under hydrothermal condition. The crystal structures of them were determined by single-crystal X-ray diffraction. And it has been proved that complex 1 and 3 were simple mononuclear compounds, complex 2, 4 and 5 were multinuclear compounds and complex 6 and 7 were coordination polymers.In chapter 3, seven novel coordination polymers of 4'-(2-pyridyl)-2,2':6',2"-terpyridine (L1) and CuCN were obtained by hydrothermal and solventthermal methods. Single-crystal X-ray diffractions had shown that complex 8 was a 2D layer; complex 9 was a 3D network, complex 10 was interpenetrated 2D layers, complex 11 and 12 had formed two cationic coordination ligands: [Fe(L1)₂]²⁺ and [Cd(L1)₂]²⁺, respectively. At the same time, both of them had fromed an anion network of CuCN. Complex 13 and 14 were come from the reactions of L1 with CuSCN. In both of the processe, SCN^- was partly decomposed and released out CN`- to coordinate with Cu. It has been proved that compex 13 was a mixed-valence Cu(I)/Cu(II) compound and formed a 3D network, but complex 14 had formed a monovalence adamantine-like cluster: Cu₆S₄ and the clusters act as six-connected nods to form a 3D α-Polonium network.