Syntheses, Crystal Structuers And Spectral Properties Of Co????Ni????Cu??? And Zn??? Complexes Based On N₂O₂ Bisoxime Ligands

Salen-type complexes, based on the development of the tetradentate schiff base, which are widely applied in many fields because of their advantages of structure and synthetic procedures, for instance, as effective and multifunctional catalysts, practical nonlinear optical materials, excellent magnetic materials, models of reaction centers of metalloenzymes, and more widely applied in biological fields. Salen-type ligands are easily obtained by the reaction of salicylaldehyde or its derivatives with diamines, coordinate to transition matal ions used to obtain mono-, di- and multinuclear complexes.In this paper, three asymmetric and one symmetric Salamo-type ligands have been synthesized based on 3,5-dichlorosalicylaldehyde and different salicylaldehyde derivatives.The ligands are:4',6'-dichloro-2,2'-[1,1'-?ethylenedioxydinitrilo?ethylidynemethylidyne]diphenol?H₂L¹?,4',6'-dichloro-2,2'-[1,1'-?1,3-propylenedioxydinitrilo?ethylidynemethylidyne]diphenol?H₂L²?,4,6-dichloro-5?-?N,N?-diethylamine?-2,2?-[ethylenedioxybis?nitrilomethylidyne?]diphenol?H₂L⁴?, 4,4',6,6'-tetrachloro-2,2'-[1,3-propylenedioxybis?nitrilomethylidyne?]diphenol?H₂L³?,which were characterized by a series of physical and chemical analysis methods.Seven transition metal complexes have been synthesized by the reaction of these ligands with Co?OAc?₂�4H₂O, Ni?OAc?₂�4H₂O, Cu?OAc?₂�H₂O and Zn?OAc?₂�2H₂O, respectively.They all have been obtained by means of naturally evaporation of solvents. They are[Cu?L¹?]?1?, [Ni?L²?₂?EtOH?₂]�EtOH?2?, [Ni₇?L³?₃?MeOH?₈?H₂O?₆]?3?,[Ni₇?L³?₃?EtOH?₈?H₂O?₆]?4?, [Co₂?L⁴?₂]�2CH₃CN?5?, [Cu?L⁴?]?6?, [Zn₂?L⁴?₂]�2CH₃CN?7?,respectively. The structures of these complexes have been determined by X-ray single crystal diffraction method, the main crystal data are as follows:Complex 1: Empirical formula, C₃₄H₂₈Cl₄Cu₂N₄O₈, formula weight, 889.48, Triclinic,space group: P-1, cell parameters: a = 11.1698?10? ???, b = 11.6733?8? ???, c = 13.8734?10? ???, ?= 95.073?6?�, ? = 94.631?7?�, ? = 104.497?7?�, V = 1734.5?2? ???3, Z = 2, R1 = 0.0459, wR2 =0.0962;Complex 2: Empirical formula, C₄₄H₅₈Cl₄N₄NiO₁₂, formula weight, 1035.45, Triclinic,space group: P-1, cell parameters: a = 9.6556?10? ???, b = 11.1497?10? ???, c = 112.9384?12? ???,? = 87.729?8?�, ? = 80.977?8?�, ? = 72.862?9?�, V = 1314.6?2? ???3, Z = 1, R1 = 0.0662, wR2 =0.1670;Complex 3: Empirical formula, C₅₉H₇₂Cl₁₂N₆Ni₇O₂₆, formula weight, 2117.46, Triclinic,space group: P-1, cell parameters: a = 14.124?4? ???, b = 16.699?5? ???, c = 19.157?5? ???, ? =99.187?4?�, ? = 95.340?4?�, ? = 92.683?5?�, V = 4432?2? ???3, Z = 2, R1 = 0.0880, wR2 = 0.1829;Complex 4: Empirical formula, C₆₃H₆₆Cl₁₂N₆Ni₇O₂₆, formula weight, 2159.58, Triclinic,space group: P-31 c, cell parameters: a = 17.371?2? ???, b = 17.371?2? ???, c = 19.1045?17? ???, ?= 90�, ? = 90�, ? = 120�, V = 4992.5?14? ???3, Z = 2, R1 = 0.0687, wR2 = 0.2051;Complex 5: Empirical formula, C₄₄H₄₈Cl₄Co₂N₈O₈, formula weight, 1076.56, Triclinic,space group: P-1, cell parameters: a = 9.6982?3? ???, b = 11.1361?8? ???, c = 23.0777?8? ???, ? =87.778?4?�, ? = 85.560?3?�, ? = 73.479?5?�, V = 2382.0?2? ???3, Z = 2, R1 = 0.0739, wR2 =0.1904;Complex 6: Empirical formula, C₂₀H₂₁Cl₂CuN₃O₄, formula weight, 501.84, Monoclinic,space group: P21/c, cell parameters: a = 10.7343?19? ???, b = 16.2871?8? ???, c = 16.272?3? ???, ?= 133.20?3?�, V = 2073.8?12? ???3,Z = 4, R1 = 0.0442, wR2 = 0.0940;Complex 7: Empirical formula, C₄₄H₄₈Cl₄Zn₂N₈O₈, formula weight, 1089.44, Triclinic,space group: P-1, cell parameters: a = 9.873?4? ???, b = 11.223?4? ???, c = 23.119?9? ???, ? =87.920?7?�, ? = 85.524?7?�, ? = 73.177?7?�, V = 2444.3?16? ???3, Z = 2, R1 = 0.0588, wR2 =0.1497;...