Synthesis And Structure Of Copper Coordination Complexes Based On Imidazolyl-Terpyridine Ligands

We have focused on the design and the synthesis of a series of 4'-(imidazolyl)-terpyridine and their CuX (X=Cl-, Br-, I-, SCN-) coordination complexes by hydrothermal or solventhermal in this work. By alternating the tempreture, stoichiometric metal/ligand ratiol, anion, the compounds, as expected, were successfully developed from simply discrete unit to one-dimensional chains, two-dimensional layers, and three-dimensional network. The complexes were determined by FTIR and Single Crystal X-ray Diffraction. The synthesis of these compounds may provide a new approach for the construction of coordination polymers of 4'-imidazolyl 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 current development of terpyridine, especially the synthises, survey of 4'-functionallized terpyridine coordination compounds and studies on the utility of terpyridine derivation. We also introduce the coordination modes of thiocynate and the inorganic framework of CuSCN in coordination polymers synthesized by our group. Finally, the meaning of this work was also narrated.In chapter 2, we intronduce synthesis of 4'-(2-imidazolyl)-2,2':6',2"-terpyridine (HL1) and copper coordination complexes. Six novel complexes of HL1 and CuX were prepared under hydrothermal condition: [Cu2(HL1)Cl4] (1), [Cu2(HL1)Cl3·0.5CH3OH]n (2), [Cu5(HL1)2I6]n] (3), [Cu(L1)]n (4), [Cu3(HL1)Br4]n (5), [Cu2(L1)Cl2]n (6). The crystal structures of them were determined by single-crystal X-ray diffraction. We modulated the coordination modes of imidazole by changing the reaction temperature and ratio for HL1 can also be chelate or bridge ligand. Thus, we successfully developed the complexes from discrete dinuclear structure to two-dimension layers, in which the anion also played a key role. The coordination modes in complexes 1, 2, 3, 5 are the same. Complex 1 was simple binuclear compound. In complex 2, Cl- bridged two copper atoms to form one-dimension chain. In complex 3, 3,3'-bpy-like metalloligand was formed, and [Cu4I6]2- cluster bridged the metalloligand to generate 1D zigzag chain. The ligand in complex 4 presented coordination modes of imidazole, which bridge two copper to form a 1D chain. An independent CuBr chain existed in complex 5, and the ligand bridged the chains to generate 2D layer. Complex 6 was a 2D (6.3) layer in which five coordination points of the ligand was coordinated.In chapter 3, we introduce synthesis the framework of Itpy (4'-(imidazolyl)-2,2':6',2"-terpyridine) and CuSCN. We used two ligands: 4'-(2-imidazolyl)-2,2':6',2"-terpyridine (HL1) and 4'-(4-imidazolyl)-2,2':6',2"-terpyridine (HL2). We prepared five complexes: [Cu(HL1)(SCN)2](7), [Cu4(L1)(SCN)3(CN)·H2O]n (8), [Cu5(L1)2(SCN)4] (9), [Cu3(L1)(SCN)3]n (10), [Cu6(L2)(HL2)(SCN)7]n (11). In this chaper we study the variety of inorganic CuSCN structure by changing reaction temperature, solvent, and ratio. The single crystal X-ray diffraction proved complex 7 is mononuclear structure in which only the tridentate part coordinated to copper. In complex 8, imidazole of the ligand connected to CuSCN hexadecimal-atom ring to form a 1D double-chain, which was connected by tridentate of ligand and then generated 2D bilayer filled with solvent water molecules. There existed a 1D CuSCN wall-like chain in complex 9. The CuSCN chains were connected by ligands to form 3D network. Complex 10 is a 3D network. There existed inorganic CuSCN 2D layers can be rationalized to a (6.3) topological networks, which were connected by ligands to generate 3D network. In complex 11, there existed the ligand and deprotonated ligands. Depronated ligands connected 1D CuSCN chain to form 2D layer.