Structures And Properties Of Nitroxide Radicals-transition(Rare-earch) Metal Coordination Complexes

Two new Nitronyl nitroxide Radicals ligand (2-（4-p-propoxy）-4,4,5,5-teramethylimidazoline-1-oxyl-3-oxide（NITPhOn-Pr）,2-（4-diethylin）-4,4,5,5-teramethylimidazoline-1-oxyl-3-oxide（NITPhNEt₂） have been synthesized. They were characterizedby IR, UV, element analysis, ESR and so on. seven novel complexes of formulas[Mn₂（hfac）₄（NITPhOn-Pr）₂]·NITPhOn-Pr（1）, Co（hfac）₂（NITPhOn-Pr）₂（2）, Ni（hfac）₂（NITPhOn-Pr）₂（3）, Dy（hfac）₃（NITPhOPr）₂（4）, Tb（hfac）₃（NITPhOPr）₂（5）, Sm（hfa-c）₃（NITPhOPr）₂（6） and Mn₂（hfac）₄（NITPhNEt₂）₂（7）（Here hfac stands for hexafluoroa-c etylacetonate） have been prepared. They were characterized by IR, the structurecomposition have were maked sure through X-ray diffraction technique. In Therare-earth compl exes, Each central ion have eight coordination sites, six oxygen atomcome from three hfacs, the others two oxygen atom come from two radicals. Thetransition metal ions have six coordination sites, owning Eight octahedral geometry.As the special structure,the two Mn-complexes both are binuclear molecule, another,in the [Mn₂（hfac）₄（NITPhOn-Pr）₂]·NITPhOn-Pr（1） complexe, there are a free radical.The thermal properties of complexes Dy（4）, Sm（6） were investigated bysimultaneous TG/DSC techniques. We simply research the magnetic property of threerare-earth and one transition metal complexes.Heat capacities of the four complexes ([Mn₂（hfac）₄（NITPhOn-Pr）₂]·NITPhOn-Pr（1）, Dy（hfac）₃（NITPhOn-Pr）₂（4）, Tb（hfac）₃（NITPhOn-Pr）₂（5）, Sm（hfac）₃（NITPhOn-Pr）₂（6） were measured by differential scanning calorimetry （DSC）. The values ofthe experimental heat capacities were fitted to a polynomial equation with theleast-squares method. Besides, the smoothed heat capacities and thermodynamicfunctions （HT-H298.15K）,（ST-S298.15K）, and （GT-G298.15K） were calculated Throughrelevant equations.