利用水熱與離子熔液法合成過渡金屬與鑭系元素的雙膦酸聚合物

Hydrothermal and Ionothermal Synthesis, Crystal Structures and Properties of Copper Diphosphonates and Lanthanide Oxalatodiphosphonates

鍾維修(Wei-hsiu Chung)

指導教授 ： 李光華

國立中央大學/理學院/化學系/碩士(2008年)

摘要

本論文主要分為兩個部份 : 第一部分研究利用中溫水熱法合成一新穎化合物 Cu4(H2O)5(hedp)2(4,4’-bpy) ; 第二部份則利用離子熱法合成四個新穎鑭系金屬草酸雙膦酸鹽化合物，分為 A、B 兩個系統 : 系統 A 為(H2bpy)0.5[Ln(C2O4)(hedpH2)]•H2O [ Ln = Pr(A1) and Nd (A2) ] ; 系統 B 為(H2DABCO)0.5[Ln(C2O4)(hedpH2)]•H2O [ Ln = Pr(B1) and Nd (B2) ] 。藉由一系列鑑定方法，包括以 X 光單晶繞射法決定出化合物的結構與化學式，再搭配元素分析、紅外線光譜、粉末繞射、熱重分析及超導量子干涉等方法進行結構組成分析、熱穩定性、熱分解反應及磁性等研究。 化合物 Cu4(H2O)5(hedp)2(4,4’-bpy) 中銅均為五配位，和雙膦酸鍵結形成像階梯狀的鏈，錬與鏈之間由4,4’-雙吡啶連接形成一 Z 字型二维層狀結構。在系統 A、B 中，所有的 Ln 均為八配位，和雙膦酸及草酸形成二维層狀結構，在層與層之間存在著胺陽離子和結晶水。 在磁性方面，化合物 Cu4(H2O)5(hedp)2(4,4’-bpy)、B1 和 B2 皆為反鐵磁性，Cu4(H2O)5(hedp)2(4,4’-bpy) 的 μeff = 2.00 μb ； B1 的 μeff = 3.71 μb ；B2 的 μeff = 3.55 μb，皆與其理論值接近。化合物 Cu4(H2O)5(hedp)2(4,4’-bpy) 由 EPR 及變溫磁性測量結果可證實所有銅原子均為帶正二價原子。

關鍵字

雙膦酸 ； 磁性 ； 離子液體 ； 鑭系金屬 ； 離子熔液 ； 水熱合成

並列摘要

A new compound Cu4(H2O)5(hedp)2(4,4’-bpy) has been synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction and thermogravimetric analysis . It has a layer structure in wich the ladder-like chains of { Cu4(H2O)5(hedp)2 } are connected by 4,4’-bpy to form a 2-D framefork. We studied the EPR and magnetic properties of this compound . It is antiferromagnetism. The measured g-value is 2.158 at room temperature and 2.155 at 77K, and the μeff is 2.00 μb ; they are very close to the theoretical values.
Another four new compounds, (H2bpy)0.5[Ln(C2O4)(hedpH2)]•H2O [ Ln = Pr (A1) and Nd (A2) ] and (H2DABCO)0.5[Ln(C2O4)(hedpH2)]•H2O [ Ln = Pr (B1) and Nd (B2) ], have been synthesized by ionothermal method and characterized by single-crystal X-ray diffraction and thermogravimetric analysis . Compounds A1 and A2 are isostructure, and compounds B1 and B2 are isostructure ,the structures of the four compounds are similar. The LnO8 is chelated by diphosphonate and oxalate to form 2-D layer framefork structures, and there are ammonium ions and waters between layers. They are the first examples of lanthanide oxalate-diphosphonate.
We studied magnetic properties of compounds B1 and B2. They are both antiferromagnetism. The μeff of B1 is 3.71μb and the the μeff of B2 is 3.551μb ; both are very close to the theoretical values.

並列關鍵字

antiferromagnetism ； EPR ； ionothermal ； oxalate-diphosphonate ； lanthanide ； hydrothermal

參考文獻

1. Smith, J. V. Chem. Rev. 1998, 88, 149.

2. Julien, C. Mater. Science and Engineering 1990, B6, 9.

5. Sharrock, M. P. MRS Bulletin. 1990, March, 53.

6. Riou, D.; Raveau, B.; Acta crystallogr., Sect. C, 1991, 47, 1708.

7. Moore, P. B.;Araki, T. Inorg. Chem. 1976, 15, 316.