Structures and Magnetic Properties of Imino/Nitronyl Nitroxide Radicals and Their Metal Complexes and Cyano-Bridged of Lanthanide Complexes.
| Autor: | Hsin-Huang Lin, 林信宏 |
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| Rok vydání: | 2005 |
| Druh dokumentu: | 學位論文 ; thesis |
| Popis: | 93 The present thesis has been divided into two parts: PartⅠ: Preparations, structures and magnetic properties of the free radicals of nitronyl nitroxide and imino nitroxide and their metal complexes have been reported. The temperature dependence of magnetic properties of these free radicals and their metal complexes are measured, the magneto-structural correlations also have been discussed. At first, twelve nitronyl/imino nitroxide derivatives are prepared, in which the crystal structures of the free radical ligands of NITpPy、NITmPy、NITpBA、IM-pBA、NITmBA、NITpAH have determined by X-ray diffraction. The temperature dependence of the magnetic susceptibility measurements of these twelve radical ligands and their seven-teen metal complexes are measured. The results are described at the followings: (1) only NITpPy and IM-pBA exhibit a weak ferromagnetic coupling and the others are all in antiferromagnetic coupling. (2) nine complexes of [Cu(CHCl2COO)2(NITmPy)2(H2O)2], [Mn(NITpPy)2(N(CN)2)2(H2O)2], [Mn(NITpPy)4(N3)2], [Cu(hfac)2(NITmPy)2], [Cu(NIT-tz)2(N3)2], [Gd2(NITpPy)4(N(CN)2)4(OH)2], [Ag(NITpBA)], [Ag(IM-mPy)(NO3)], [Ag1.5(IM-oBA)(0.5NO3)] exhibit ferromagnetic coupling, whereas [Co(NITpPy)2(N(CN)2)2(H2O)2], [Mn(NIT-Ida)2Cl2], [Ni(NIT-tz)2Cl2], [Mn(NIT-tz)(N(CN)2)2], [Co(NITpPy)4(N3)2], [Ag(IM-Py)(NO3)] and [Ni(NITpPy)4(N3)2] are antiferromagnetic coupling. The magnetic exchange mechanism for these complexes have been discussed. In addition, the result also show that magnetic interaction through the N(CN)2- bridge are very weak. (3) [Pt(II)(IM-oPy)Cl2] coordinate environment is quite similar anticancer drug, so that the interaction with Ф174 double stranded DNA has been studied to understand its response mechanism. Part II : eleven discrete heterdinuclear [Ln(dmf)4(H2O)3Fe(CN)6]•H2O ( Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb ), two [Ln(dmf)4(H2O)3Co(CN)6]•H2O ( Ln = Pr and Er ), 1-D [Ln(dmf)4(H2O)2Cr(CN)6]•H2O ( Ln = Pr and Sm), [Gd(o-phen)(dmf)2(H2O)2-Fe(CN)6]•3H2O, and 3-D [DyFe(CN)6(H2O)2]•H2O complexes with Ln-NC-M(3d) have been prepared and structural characterized. The magnetic properties for these seven teen complexes have been determined by temperature dependence of magnetic susceptibility measurements. The intramolecular anti- and ferromagnetic couplings between Ln-NC-M(3d) are dependence of electron configuration of 4 fn. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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