本文研究為二磷酸基的有機配子1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb)與過渡金屬離子 (CoII、MnII)和鹼土族離子(BaII),在調控的酸鹼及溫度環境下,進行自組裝合成,製備有機-無機金屬之配位聚合物。 以H4bmpb與過渡金屬離子(MnII、CoII)與鹼土族離子(BaII)利用室溫反應方式,在調控pH值下,得到兩個相類似結構的一維鍊狀配位聚合物 {[Co(H2bmpb)(H2O)4]•2H2O}n (1)、{[Mn(H2bmpb)(H2O)4]•2H2O}n (2),及得到一個共結晶複合物{[Ba2(H2O)12•(bmpb)]•4H2O} (3),一併探討其結構特性與物性分析。利用H4bmpb與過渡金屬離子(CoII)分別與4,4'-bipyridine配子及2,2'-bipyridine配子進行自組裝合成。利用室溫下反應,得到二維平面結構{[Co(H2bmpb)(4,4-bpy)(H2O)2]•2H2O}n (4),及在恆溫60℃得到一維鍊狀配位聚合物 {[Co(H2bmpb)(2,2-bpy)(H2O)2]•2H2O}n (5),最後一併探討其結構特性與物性分析。
In this thesis, a bis-phosphonate acid ligand 1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb) was reacted with transition-metal ions (MnII, CoII), and alkaline earth ions (BaII), at different temperatures and at different pH values, resulting in the formation of five coordination polymers 1-5. When the H4bmpb ligand was reacted with transition-metal ions (MnII, CoII), three coordination polymers were produced. Compounds 1 and 2 were prepared under different reaction conditions at different pH values. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction analyses. The compounds are isostructures and adopt a 1D chain topology. Compound 3 was obtained as a co-crystal. The thermal stability and physical properties of the complexes were also examined. Compounds 4 and 5 were produced by the reaction of H4bmpb with a transition-metal ion (CoII) in the presence of 4,4'-bipyridine or 2,2'-bipyridine. Compound 4 is a 2D coordination polymer. The 2D layers are further stacked into a 3D MOF. However, when the temperature was increased to 60 °C, compound 5 was produced. This compound is a 1D chain and the chains are further linked into a 2D sheet. The structures, thermal stabilities and physical properties of products 1-5 are discussed in this thesis.
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