| Abstract: | 本篇論文分成兩個部分，第一部分使用NiCl2•6H2O、NiBr2•H2O以及NiSO4•6H2O與氨基三唑雙?啶配位子(H2L, N2,N2-dibenzyl-N4,N6-bis((pyridin-2-yl)methyl)-1,3,5-triazine-2,4,6-triamine)，以水熱法製備出化合物1~3，{[NH2(CH3)2]2[Ni5Cl10(H2L)2(OH)2]} (1)、{[Ni6Br10(OH)2(THF)2(H2L)2]} (2)、{[Ni2(SO4)2(H2L)2(MeOH)4]} (3)，化合物1中，鎳金屬間以氯原子和氫氧根離子橋接形成五核鎳化合物。化合物2中，鎳金屬之間以溴原子和氫氧根離子橋接形成三核鎳次單元，次單元間利用兩個配位子來連接形成六核鎳化合物。化合物3中，鎳金屬間利用兩個硫酸根 (SO42-) 來連接形成二核鎳化合物。化合物1~3的結構以及磁性性質，將會在本論文中進行討論。 第二部分使用Cu(OAc)2•H2O和Cu(ClO4)2•6H2O與H2L反應並加入過氯酸根、苯甲酸根以及丙酸根當作橋樑基，得到化合物4~7，{[Cu3(HL)(CH3COO)4(OH)]•H2O} (4)、{[Cu8(H2L)2(ClO4)4(OH)6(i-PrOH)2(PhCO2)4](ClO4)2•2(i-PrOH)•2(CH2Cl2)} (5)、{[Cu12O3(HL)2(L2)2(CH3CO2)8(OH)2](ClO4)2•4H2O} (6)、{[Cu12O3(HL)2(L2)2(C2H5CO2)8(OH)2](ClO4)2•4H2O} (7)。化合物4中，銅金屬之間以醋酸根以及氫氧根橋接形成三核銅化合物。化合物5中，銅金屬之間以過氯酸根、苯甲酸根以及氫氧根離子橋接形成八核銅化合物。化合物6和7結構上相似，藉由羧酸根與氧原子橋接形成十二核銅化合物，在結構中含有兩種不同配位模式的H2L (?3-HL-?5-N,N′:N′′:N′′′,N′′′′以及?3-L-?5-N,N′:N′′:N′′′,N′′′′)。化合物4~7的結構以及磁性性質，將會在本論文中進行討論。
This study contains two parts. In the first part, three complexs, {[NH2(CH3)2]2•[Ni5Cl10(H2L)2(OH)2]} (1), {[Ni6Br10(OH)2(THF)2(H2L)2]} (2), {[Ni2(SO4)2(H2L)2(MeOH)4]} (3) have been synthesized from the hydrothermal method from the reactions of N2,N2-dibenzyl-N4,N6-bis((pyridin-2-yl)methyl)-1,3,5-triazine-2,4,6-triamine (H2L) and NiCl2•6H2O, NiBr2•6H2O and NiSO4•6H2O, respectively. Complex 1 is a Ni5 cluster, which is bridged by hydroxide, chloride and H2L ligand. Complex 2 contains two Ni3 subbuilding units, where the Ni3 cluster is bridged by hydroxide ions and bromide. Two Ni3 clusters are linked into Ni6 cluster by H2L ligand. Complex 3 is a Ni2 cluster by hold two sulfate ions and H2L ligand. The structures and magnetic properties of Complexes 1~3 were discussed. In the second parts, four complexs, {[Cu3(HL)(CH3COO)4(OH)]•H2O} (4), {[Cu8(H2L)2(ClO4)4(OH)6(i-PrOH)2(PhCO2)4](ClO4)2•2(i-PrOH)•2(CH2Cl2)} (5), {[Cu12O3(HL)2(L2)2(CH3CO2)8(OH)2](ClO4)2•4H2O} (6), {[Cu12O3(HL)2(L2)2(C2H5CO2)8(OH)2](ClO4)2•4H2O} (7) were synthesized from the reactions of H2L ligand with Cu(OAc)2•H2O, Cu(ClO4)2•6H2O and one of perchlorate ion, benzoate and propionate ions, respectively. Complex 4 is a Cu3 cluster, which is bridged by hydroxide, acetate and H2L ligand. Complex 5 is a Cu8 cluster hold by hydroxide ions, perchlorate ions, benzoate and H2L ligand. Complexes 6 and 7 are similar to the structure. The only difference is carboxylate species. The complexes are comprised of two different modes of H2L ligand (?3-HL-?5-N,N′:N′′:N′′′,N′′′′-mode and ?3-L-?5-N,N′:N′′:N′′′,N′′′′-mode). The structures and magnetic properties of Complexes 4~7 were discussed. |
