The Synthesis Of New Complexes Of Phenanthroline Derivatives As Ligands, Characterization, And Nature Study

In this dissertation ten novel coordination complexes have been designed and synthesized dealing with the derivatives of 1,10-phenanthroline as ligands and the ten complexes include the mononuclear Cu(II) complex [Cu(PhenOH)(OCH₃)(HOCH₃)SCN] (1) with 2-hydroxyl-1,10-phenanthroline, deprotonated methanol and methanol as terminal ligands; mono-nuclear Cu(II) complex [Cu(PhenBipy)(ONO2)]NO3 (2) with 1-(2-(2-oxopyridin-1(2H)-yl)-1,10-phenanthrolin-9-yl)pyridine-2(1H)-one and nitrate as ligands; binuclear Fe(III) complex [Fe₂(μ-O)(Phenom)₂(Cl)₄]1.5CH₃CN (3) with single oxygen anion as bridge ligand and 2-methoxy-1,10-phenanthroline and chloride anion as terminal ligands; two-dimensional Co(II) coordination polymer {Co[μ1,5-N(CN)₂](Phenom)}n (4) with dicyanamide anion as bridge ligand and 2-methoxy-1,10-phenanthroline as terminal ligand; mono-nuclear Co(II) and mono-nuclear Ni(II) complexes [Co(PhenPz)(OOCCH2COO)(H2O)] (5) and [Ni(PhenPz)(OOCCH2COO)(H2O)] (6) with 2-(1H-pyrazol^-1-yl)-1,10-phenanthroline and propanedionate divalent anion as capped ligands; mono-nuclear Zn(II) complexes [Zn(Phenom)Cl2] (7), [Zn(Phenom)(NCS)₂] (8) and[Zn(Phenom)(NCS)Cl][Zn(Phenom)Cl2]CH₃CN (9) with 2-methoxy-1,10-phenanthroline as ligand; mono-nuclear Ni(II) complex [Ni(PhenDM)₂(NCS)₂]2CH₃OH (10) with thiocyanate anion and 2-(dimethyl)amine-1,10-phenanthroline as terminal ligands. The ten complexes were characterized by infrared spectra, elemental analysis and X-ray crystallographic analysis. The variable-temperature magnetic susceptibilities for complex (1), (2), (3) and (4) were measured at 2-300 K. Fitting based on the data of the susceptibilities of complex 1 reveals that there is a strong ferromagnetic coupling with 2J = 100.08 cm3-mol^-1 between adjacent mono-nuclear Cu(II) complexes due toπ-πstacking. It is the first example that deals with strong ferromagnetic coupling due toπ-πstacking in non-radial group complexes. The data of variable-temperature susceptibilities of complex 2 indicate that there exists a strong anti-ferromagnetic interaction between the adjacent mono-nuclear Cu(II) complexes due toπ-πstacking. For complex 3 the fitting based binuclear Fe(III) formula displays the there is a medium ferromagnetic exchange with 2J = -235.52 cm3-mol^-1 between the bridged Fe(III) ions. For complex 4 the Weiss constant based on the equationχm = C/(T-θ) gives a small negative value (θ= -8.93 K), which indicates that there is a weak anti-ferromagnetic interaction with between bridged Co(II) ions. The crystal structure of complex 4 exhibits the right-handed helical chain and the left-handed helical chain that consist of dicyanamide bridge ligand and Co(II) ion, it is the first complex that possesses both right-handed helical chain and left-handed helical chain in complexes with dicyanamide anion as ligand. The relevant correlation dealing with coordination specialties and the crystal structures for complexes 5, 6, 7, 8, 9 and 10 were discussed. The studied results of this dissertation will benefit the understanding the magnetic coupling mechanism forπ-πstacking system and it also will benefit the synthesis ideal molecule-based magnets. And at the same time this dissertation also will contribute to the synthesis of novel complexes dealing with derivatives of 1,10-phenanthroline.