| This thesis focuses on the design of functionalized terpyridines, the preparartion of some mixed-valence Cuâ… Cuâ…¡-terpyridyl complexes and terpyridyl-Agâ… or Znâ…¡ d10 metal complexes, and the discussion of the relations between structures and magnetism or photoluminescence. The work provides some new methods and thoughts in the controlled design of functional coordination compounds. 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 survey of terpyridyl coordination compounds and studies on quarter, quinque and sexipyridine, in addition, the meaning of this work was also described.In chapter 2, eight novel mixed-valence Cuâ… Cuâ…¡ or Cuâ… Cuâ… Cuâ…¡ complexes containing ligands 4'-(4-pyridyl)-2,2':6',2"-terpyridine (L1), 4'-(3-pyridyl)-2,2':6',2"-terpyridine (L2), 4'-(2-pyridyl)-2,2':6',2"-terpyridine (L3) and 4'-phenyl-2,2':6',2"-terpyridine (L4) were prepared under the hydrothermal or layering methods. Their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl2·2H2O or Cu(CH3COO)2·H2O with L1-L4 ligands and NH4SCN, KI or KBr under hydrothermal conditions afforded five 1-D mixed-valence Cuâ… Cuâ…¡ complexes: [Cu2(L1)(μ-1,1-SCN)(μ-Cl)Cl]n (1), [Cu2(L1)(μ-I)2Cl]n (2), [Cu2(L1)(μ-Br)2Br]n (3), [Cu2(L1)(μ-1,3-SCN)2(SCN)]n (4), [Cu2(L3)(μ-1,3-SCN)3]n (6) and two Cuâ… Cuâ… Cuâ…¡ complexes: [Cuâ…¡(L2)2]n[Cu2â… (SCN)4]n (7) and [Cuâ…¡(L4)2]n[Cuâ… 2(SCN)4]n (8). Complex [Cu2(L1)(μ-1,3-SCN)2.5]n·0.5(SCN)n (5) was prepared by layering with CuSCN and L1, which shows a 2-D bilayer structure. In complexes 1-5, L1 ligand and halogen or pseudohalogen X (X = C1, Br, I, SCN) linked between monovalent and divalent copper centers resulting in the formation of mixed-valence rectangular grid-type M4L4 (1-4) or M6L6 (6) building blocks, which was further linked by SCN (in 1, 4, 5), I (in 2) or Br (in 3) to form 1- or 2-D polymers. The sizes of M4L4 units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH3COO)2·H2O with L3 and NH4SCN under hydrothermal conditions gave complex 6. Unlike those in complexes 1-5, the structure was constructed by SCN groups, and the pendant pyridine of L3 left uncoordinated. The structures of-complexes 7 and 8 are verysimilar, which were composed of mononuclear [Cu(L)2]2+(L = L2> L4) cations and two 1-D [Cu'tSCN^],,"' anion chains.The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence CulCu11 electronic structure.In chapter 3, several terpyridyl-Ag'/Zn" d10 metal complexes were introduced. Complexes [Ag(Ll)(CH3CN)]PF6-CH3CN (9) and [Ag4(Ll)4](PF6)4-(CH3COCH3)2 (10) [L - 4'-phenyl-2, 2':6',2"-terpyridine] were obtained from acetonitrile and acetone, respectively. X-ray crystallography showed that in 10, the Ag atoms are two or four-coordinate, and the LI ligand bridges between two Ag centers coordinating as a bidentate unit to one center and a monodentate to the other, forming a double-helical dimmer cation. Dimers were connected by ligand unsupported Ag-Ag metal bonding to form tetranuclear units and then further aggregated to 1-D infinite metal string by weak Ag--Ag interactions. Along Ag direction, Ag—Ag—Ag—Ag angles are 180.0°. 9 and 10 shows strong room-temperature emission in fluid solution and solid state upon excitation at 335 nm. Complex 10 was disaggregated into 9 in acetonitrile based on the comparison of their photo luminescence in acetonitrile.Secondly, a new ligand 4'-phenyl-4,2':6',4"-terpyridine (L2) and its zinc complex [Zn(L2)Cl2]w (11) were prepared and structurally characterized by single-crystal X-ray diffraction. In L2, the three pyridyl rings are non-planar. In 11, the ligand L2 links two zinc atoms through two terminal pyridines to construct a 1-D helical polymer chain with the helical pitch of 19.301 A. Compounds L2 and 11 display strong green and blue fluorescence in solid state at room temperature, respectively, upon excited at 400 nm.
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