Syntheses, Crystal Structuers And Spectral Properties Of Salamo-type Co(?)?Ni(?)?Cu(?)?Zn(?) And Cd(?) Complexes

Transition metal complexes with Salen-type ligands have been applied in all kinds of fields. Some complexes can be used in molecule recognition, catalysts, magnetism materials,and they can also be applied to the fields such as analytical chemistry and biochemistry and so on. Therefore, the design and synthesis of asymmetrical Salamo-type compounds have the important significance, because they are as a kind of important Salen-type compounds and potential applications in luminescent device have been also observed for Salamo-type compounds and their transition metal complexes. The asymmetrical configuration can afford more opportunities of a greater structural variation and coordination polymers, which could be expected to lead to novel characteristics and better enantioselectivities when compared with their symmetrical counterparts. As selective synthesis of asymmetrical Salamo-type ligands is important because electronic and steric effect of the ligands on Salen-metal-assisted catalysis may be controlled by introduction of different substituents into the two benzene rings.In this paper, firstly we synthesised a diamine derivative 1,2-bis?aminooxy? ethane. The reaction of 2-hydroxy-3-methoxybenzaldehyde with excess 1,2-bis?aminooxy? ethane gave the desired mono-oxime, then the mono-oxime reacts with different salicylaldehyde derivatives. Thus we can obtain three kinds of unsymmetrical salamo ligands: H₄L¹, H₃L² and H₃L³. In a nonaqueous solvent, the transition metal salts Ni?OAc?₂?4H₂O, Co?OAc?₂?4H₂O,Cu?OAc?₂?H₂O, Cd?OAc?₂?2H₂O and Zn?OAc?₂?2H₂O were mixed with the above organic ligands. Nine complexes have been crystaled by methods of naturally evaporation:[{Cu?HL¹??OAc?Cu}₂]�CH₃OH?1?, [Zn?HL¹??OAc?Zn?CH₃CH₂OH?]?2?,[{Cd?HL¹??OAc?Cd?CH₃CH₂OH?}₂]�2CHCl₃?3?, [Co?L²??OAc?Co?CH₃CH₂OH?₂]?4?,[Ni?L²??OAc?Ni?H₂O?₂]?5?,[Zn?L²??OAc?Zn?CH₃OH?]?6?, [{Cd?L²??OAc?Cd?CH₃OH?}₂]?7?,[{Cu?L³??OAc?Cu?H₂O?}₂]?8? and [{Zn?L³??OAc?Zn?H₂O?}₂]?9?, respectively. The compounds and these complexes were characterizated by using elemental analysis, 1H NMR,solubility experiments, IR, UV-Vis and other analytical testing methods conventionally.Meanwhile, some complexes fluorescence properties were studied to explore the mechanism of photoluminescence. Simultaneously, the formulas and steric configurations of those complexes have been determined by X-ray crystal diffraction and their supramolecular structures were studied in detail.The main crystal datas are as following:complex 1: Empirical formula, C₅₅H₅₄Cu₄N6O₁₉, formula weight, 1357.20, Triclinic,space group: P-1, cell parameters: a = 9.8721?4? ?, b = 15.5004?8? ?, c = 19.2091?8? ?, ? =95.063?4? �, ? = 97.008?4? �, ? = 94.171?4?�, V = 2895.7?2? ?3, Z = 2, R₁ = 0.0713, wR₂ =0.1838;complex 2: Empirical formula, C₂₉H₃₁Zn₂N₃O₁₀, formula weight, 712.31, Monoclinic,space group: P2?1?/c, cell parameters: a = 14.8512?5? ?, b = 13.4320?7? ?, c = 15.7579?7? ?,? = 90�, ? = 111.368?5?�, ? = 90�, V = 2927.3?2? ?3, Z = 4, R₁ = 0.0531, wR₂ = 0.0797;complex 3: Empirical formula, C₆₀H₆₄Cd₄Cl₆N₆O₂₀, formula weight, 1851.46, Triclinic,space group: P-1, cell parameters: a = 9.6876?10? ?, b = 12.9281?10? ?, c = 14.2601?10? ?, ?= 104.768?6?�, ? = 94.128?7?�, ? = 93.940?7?�, V = 1715.4?3? ?3, Z = 1, R₁ = 0.0426, wR₂ =0.0843;complex 4: Empirical formula, C₃₁H₃₅Br₂Co₂N₃O₁₀, formula weight, 887.30, Monoclinic,space group: C2/c, cell parameters: a = 10.0471?5? ?, b = 31.7717?19? ?, c = 24.9332?14? ?,? = 90�, ? = 92.652?5?�, ? = 90�, V = 7950.5?8? ?3, Z = 8, R₁ = 0.0782, wR₂ = 0.1945;complex 5: Empirical formula, C₂₉H₃₃Br₂Ni₂N₃O₁₁, formula weight, 876.82, Triclinic,space group: P-1, cell parameters: a = 9.4737?7? ?, b = 11.3570?9? ?, c = 16.733?2? ?, ? =101.206?10?�, ? = 90.044?9?�, ? = 98.867?7?�, V = 1744.1?3? ?3, Z = 2, R₁ = 0.1155, wR₂ =0.2655;complex 6: Empirical formula, C₂₈H₂₇Br₂Zn₂N₃O₉, formula weight, 840.09, Triclinic,space group: P-1, cell parameters: a = 14.2905?13? ?, b = 15.1159?16? ?, c = 15.6405?13? ?,? = 93.113?8?�, ? = 93.401?7?�, ? = 93.276?8?�, V = 3361.4?5? ?3, Z = 4, R₁ = 0.0739, wR₂ =0.1402;complex 7: Empirical formula, C₂₈H₂₇Br₂Cd₂N₃O₉, formula weight, 934.14,Orthorhombic, space group: Pbca, cell parameters: a = 16.9945?6? ?, b = 17.4212?5? ?, c =19.9811?5? ?, ? = 90�, ? = 90�, ? = 90�, V = 5915.7?3? ?3, Z = 8, R₁ = 0.0438, wR₂ = 0.0773;complex 8: Empirical formula, C₁₉H₂₀Cu₂N₂O₉, formula weight, 547.45, Triclinic, space group: P-1, cell parameters: a = 9.8760?8? ?, b = 10.3919?10? ?, c = 12.2540?10? ?, ? =88.717?7?�, ? = 75.141?7?�, ? = 73.324?8?�, V = 1162.67?17? ?3, Z = 2, R₁ = 0.0509, wR₂ =0.1139;complex 9: Empirical formula, C₃₈H₄₀Zn₄N₄O₁₈, formula weight, 1102.22, Orthorhombic,space group: Pca21, cell parameters: a = 16.8733?7? ?, b = 14.6131?7? ?, c = 19.5751?9? ?, ?= 90�, ? = 90�, ? = 90�, V = 4826.7?4? ?3, Z = 4, R₁ = 0.0714, wR₂ = 0.1573.