Synthesis, Crystal Structure And Spectral Properties Of 3d, 3d-2s And 3d-4f Complexes With Salamo-type Ligand

In the aspect of structure, the oxime complexes are evolved from symmetric to asymmetric, from homonuclear to heteronuclear, and from single to double to more than two to one, meanwhile, the synthesis methods are various. The ligands and its complexes have wide application prospect in many fields, which have two oximes or more, the macrocyclic complexes of which has played a very important role in the field of catalysis, semiconductor, fluorescent material, and its biological. This is due to the central ions magnetic spin exchange interaction, which makes the complexes have nonlinear optical properties and excellent magnetic properties.In this context, a novel type of bis?salamo?-type ligand has been synthesized and characterized by IR, UV-vis spectra and elemental analyses which assuered the clathrate compound is the target product. The complexes?[LZn₃?OAc?₂?CH₃OH?₂]?3CHCl₃?1?, [LZn₂Ca?OAc?₂]?CHCl₃?2?, [LZn₂Sr?OAc?₂]?3?, [LZn₂Ba?OAc?₂?CH₃OH?]?CHCl₃?4?, [LZn₂La?OAc?₃]?5?, [LZn₂Ce?OAc?₃]?6?, [LZn₂Dy?OAc?₃?CH₃OH?]?CH₂Cl₂?7?? were prepared by the reactions of the ligand with metal ions. The complexes were characterized by elemental analyses, IR and UV-vis titration, its corresponding crystal data were obtained by the X-ray diffraction. The optical properties of these complexes were further explored by fluorescence spectroscopy.[LZn₃?OAc?₂?CH₃OH?₂]?3CHCl₃: Empirical formula, C₄₁H₄₅Cl₉N₄O₁₆Zn₃, Formula weight, 965.03, Monoclinic, P21/n, Unit call dimensions: a = 14.0480?4? ?, b = 16.5494?3? ?, c = 23.6735?5? ?, ? = 100.464?2?°, Z = 4, V = 5412.2?2? ?3, R1 = 0.0519, wR2 = 0.1136.[LZn₂Ca?OAc?₂]?CHCl₃: Empirical formula, C₃₇H₃₅CaCl₃N₄O₁₄Zn₂, Formula weight, 1036.86, Triclinic,`P1, Unit call dimensions: a = 13.4794?7? ?, b = 13.6682?6? ?, c = 15.4156?9? ?, a = 85.483?4?°, ? = 65.228?5?°, ? = 65.053?5?°, Z = 2, V = 2321.6?2? ?3, R1 = 0.0524, wR2 = 0.1549.[LZn<sub>2</sub>Sr?OAc?<sub>2</sub>]: Empirical formula, C<sub>36</sub>H<sub>34</sub>N<sub>4</sub>O<sub>14</sub>SrZn<sub>2</sub>, Formula weight, 965.03, Triclinic,`P1, Unit call dimensions: a = 12.6197?14? ?, b = 13.346?2? ?, c = 15.6864?18? ?, a = 114.099?13?°, ? = 104.696?10?°, ? = 99.435?11?°, Z = 2, V = 2223.2?6? ?3, R1 = 0.0690,wR2 = 0.0926.[LZn₂Ba?OAc?₂?CH₃OH?]?CHCl₃: Empirical formula, C₃₉H₄₃BaCl₃N₄O₁₆Zn₂, Formula weight, 1198.20, Triclinic,`P1, Unit call dimensions: a = 10.6854?5? ?, b = 14.1383?7? ?, c = 16.2738?13? ?, a = 73.657?6?°, ? = 88.178?5?°, ? = 78.971?4?°, Z = 2, V = 2315.0?2? ?3, R1 = 0.0520, wR2 = 0.1453.[LZn<sub>2</sub>La?OAc?<sub>3</sub>]: Empirical formula, C<sub>38</sub>H<sub>37</sub>LaN<sub>4</sub>O<sub>16</sub>Zn<sub>2</sub>, Formula weight, 1075.36, Triclinic,`P1, Unit call dimensions: a = 10.4562?4? ?, b = 14.5979?7? ?, c = 18.4521?7? ?, a = 73.452?4?°, ? = 75.215?3?°, ? = 77.263?4?°, Z = 2, V = 2577.05?19? ?3, R1 = 0.0353, wR2 = 0.0787.[LZn₂Ce?OAc?₃]: Empirical formula, C₃₈H₃₇CeN₄O₁₆Zn₂, Formula weight, 1076.57, Triclinic,`P1, Unit call dimensions: a = 13.4231?12? ?, b = 13.5379?12? ?, c = 15.6521?13? ?, a = 64.689?9?°, ? = 78.336?8?°, ? = 70.323?8?°, Z = 2, V = 2415.4?4? ?3, R1 = 0.0717, w R2 = 0.1441.[LZn₂Dy?OAc?₃?CH₃OH?]?CH₂Cl₂: Empirical formula, C₄₀H₄₃Cl₂DyN₄O₁₇Zn₂, Formula weight, 1215.92, Monoriclinic, P21/c, Unit call dimensions: a = 12.6510?3? ?, b = 13.6894?3? ?, c = 26.8174?7? ?, ? = 103.515?3?°, Z = 4, V = 4515.77?19? ?3, R1 = 0.0402, w R2 = 0.1044.