Synthesis, Structure And Spectroscopic Study On Heteronuclear Terpyridine Complexes

The thesis focuses on the preparation of a series of Cu^â… Ni^â…¡and Cu^â… Zn^â…¡heterometallic terpyridine complexes by the design of functionalized terpyridines. Thecrystal structures of the complexes were determined by single-crystal X-raydiffraction and IR spectrometry. This work provides some new methods and thoughtsin the design and synthesis of heterometallic terpyridine complexes.In Chapter 1, the research background of the synthesis of 4'-functionallizedterpyridine and the current survey of terpyridine coordination compounds is conciselyintroduced. A survey of metalloligand is also mentioned.In Chapter 2, three novel heteronuclear Cu^â… Zn^â…¡or mixed-valence Cu^â… Cu^â…¡complexes containing ligands 4'-(4-pyridyl)-2,2':6',2"-terpyridine (L1),4'-(2-pyridyl)-2,2':6',2"-terpyridine (L2), [Cu₂Ni(L2)(μ₂-CN)₃(μ₂-Br)]_n(1),[CuNi(L1)(μ₂-CN)(μ₂-I)] (2), [Cu₂(L1)(μ₂-Cl)₃]_n (3) were prepared by the one-stephydrothermal method. Complex 1 is a 2D heteronuclear polymer formed by the 1Dheterometallic CN chains linked by Br atoms. Complex 2 is a heteromultinuclearcomplex. In mix-valence complex 3, L1 ligand and C1 atom linked betweenmonovalent and divalent copper centers resulting in the formation of mixed-valencerectangular grid-type M₄L₄ building blocks, which was further linked by Cl atom toform a 1D polymer.In Chapter 3, we have introduced the synthesis of heteronuclear terpyridinecomplex by two-step methods based on metalloligand. Two metalloligandsZn(L2)₂(BF4)₂ (4), Cd(L2)₂(PF₆)₂(H₂O) (5) were prepared firstly, then reacted withCuX (I, CN, SCN) to obtain five d¹⁰-d¹⁰ polymers. Complex 6 has a 3Dinorganic-organic hybrid structure constructed by a 2D heterometallic Cu^â… Zn^â…¡layerand linker L1. Complex 7 is a self-catenated structure formed through cross-linking oftwo cationic and one anionic networks connected by ligand-unsupported Cu…Cu andCu…C interactions. Complex 8 is a 1D chain structure built by metalloligand attachedto a CuCN chain. Similar to 8, complex 9 is also a 1D structure. In complex 10, 1D inorganic chain is formed by Cd cations and three kinds of SO₄^2-, 2D inorganic layeris formed by Cu atoms and SCN. Complex 10 is a heteroinorganic-organic hybridstructure which consists of 1D inorganic chains, 2D inorganic layers and ligand L1.