Syntheses And Structures Of The Complexes Based On Crown Ether Containing Phenol Groups

The chemistry of organic-inorganic coordination complexes has recently become area of increasing interest. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. In the thesis, we synthesized two kinds of aza-crown ether ligands: 10,21-dimethyl-3,6,14,17-tetraazatricyclo[17.3.18,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diol(H₂L) and H₂L'(see below), and studied the syntheses, structures and properties of 6 new complexes generated from aza-crown ether ligands. The compounds were characterized by IR, elemental analysis, thermogravimetric analysis (TGA), X-ray single-crystal diffraction and XRPD.1. Four new complexes generated from aza-crown ether ligand H2L and CuSO₄·5H₂O,CuCl₂·2H₂O and NiCl₂·6H₂O were synthesized: [Cu₆L₃(SO₄)₂]·SO₄·8H₂O (1),[Cu₂L(SO₄)(H₂O)]·2H₂O (2), [Cu₂LCl][Cu₂L(H₂O)₂]·3Cl·2.75H₂O (3) and [Ni₄L₂(μ-OMe)2 (μ3-OH)2]·2MeOH·2H2O (4). Their crystal structures and teamperatur-controlled syntheses were investigated.2. Two new Ni(II) complexes have been constructed using an in situ metal/ligand reaction based on aza-crown ether ligand H2L: [Ni(H₂L')]·m-BDC·3H₂O (5),[Ni(H₂L')]·p-BDC·MeOH·2H₂O (6). Their crystal structures were determined, and the oxidation-reduction properties were also investigated in detail.