多取代芳香氮氧自由基及其配合物的合成结构和磁性研究无机化学专业论文.docxVIP

AbstractIn Abstract In this paper,two new nitronyl nitroxide radicals have been synthesized successfully： NITPh-3，4一(OMe)2 (2一(3 7，4’-dimethoxyphenyl)一4，4，5，5一tetramethyl —imidazoline一1一oxyl-3一oxide)and NITPh一3-OEt一4一OMe(2一(3-ethoxy-4-methoxy —phenyl)．4，4，5，5一tetramethylimidazoline一1一oxyl一3-oxide)．They were characterized by IR，UV-vis，Elemental analysis，XRD，ESR and single—crystal X—ray diffraction． Reacted with Ln(hfac)3’2H20[Ln=Sm，Eu，Gd，Tb，Dy；hfac 2 hexafiuoroacetyl -acetonate)and Mn(hfac)2‘2H20 respectively,eleven novel complexes have been obtained：[Ln(hfac)3(NITPh一3，4一(OMe)2)2】[Ln=Sm(1)，Eu(2)，Gd(3)，Tb(4)，Dy(5)】， [Ln(hfac)3(NIPh-3-OEt-4-OMe)(IMHPh一3一OEt一4一OMe)][Ln 2=Sm(6)，Eu(7)，Gd(8)]， [Ln(hfac)3(NIPh一3一OEt-4一OMe)2】[Ln=Tb(9)，Dy(10)]and[Mn(hfac)2(IMHPh-3，4 一(OMe)2)]2(11)． Complexes 1-5 are mononuclear tri-spin structures，in which central Ln(III)ion is eight-coordinated distorted dodecahedron coordinated by two oxygen atoms from two nitroxide groups and six oxygen atoms from three hfac anions．Complexes 6-10 are also mononuclear structures，of which 9 and 10 similar to complexes 1-5． However,the prominent feature of complexes 6-8 is that a radical NITPh一3一OEt一4一OMe was reduced to IMHPh-3一OEt-4-OMe．The polyhedron around the Ln(III)ion is also an eight—coordinated distorted dodecahedron with triangular faces．In complex 11，two bridging IMHPh一3，4一(OMe)2 ligands connect two Mn(II) ions，forming a dinuclear structure，in which IMHPh一3，4一(OMe)2 is a reduced form of NITPh一3，4一(OMe)2．The central Mn(II)ions adopt six—coordinated distorted octahedron， which coordinated two bidentate hfac ligands and two IMHPh一3，4-(OMe)2 The magnetic properties of these complexes have been studied．For 2 and 7，the negative zJvalue indicates antiferromagnetic interaction between Eu(III)and radical； For 3，the positive^value indicates that there is weak ferromagnetic interaction between Gd(III)ion and the NITPh(OMeh radicals，and the negative也shows the antiferromagnetic interactio