| 摘要: | 在本論文中，是以草酸作為混合配位基，利用中溫水熱反應合成了三個新穎結構的固態化合物，這三個化合物可以分為兩類：草酸-磷酸鐵與草酸-磷酸鎵化合物。所列如下： Ⅰ、Iron oxalatophosphate 三維草酸-磷酸鐵化合物 (C4H16N3)[Fe2(C2O4)(HPO4)2(PO4)] (1) Ⅱ、Gallium oxalatophosphate 二維草酸-磷酸鎵化合物 (C4H14N2)[Ga2(C2O4)0.5(H2PO4)(PO4)2] ?2H2O (2) 三維具大孔洞草酸-磷酸鎵化合物 (C4H16N3)0.5[Ga2(C2O4)0.5(H2PO4)0.5(PO4)2] ?1.5H2O(3) 以上所列的化合物均可得到單晶，首先由X-光能量散佈光譜儀(EDX)測得晶體含有過渡金屬及磷等元素，之後由單晶X-光繞射鑑定出結構；粉末X-光繞射分析確定產物純度；元素分析(EA)確定化合物中C、N、H等元素的比例；熱重量分析(TGA)研究化合物的熱性質；超導量子干涉磁量儀(SQUID)來測量化合物的磁性現象。 化合物1是三維隧洞結構。此結構具有多方向相互貫穿的隧洞，沿a軸方向可發現十二員環隧洞，結構中的有機胺陽離子便填充於十二員環的隧洞中，另外也對化合物1做磁性的測量，得知其結構中具有反鐵磁性的交互作用。 化合物2是屬於二維層狀結構，沿c軸方向可看到其層狀架構是由兩種無限延伸鏈以相互配位的方式連接而成，兩條無限延伸鏈皆平行於a軸，憑藉著共用PO4四面體而於ab平面上形成層狀結構，有機胺陽離子便填充於層與層之間。化合物3是三維隧洞結構，基本架構是由六配位八面體GaO6利用草酸根陰離子與鄰近的GaO6八面體相互連接，形成二聚體的形式，再與GaO4四面體以共角方式與PO4四面體連接，於bc平面上形成一層狀結構，而層與層之間則是藉由H2PO4四面體相互連接而成三維隧洞，沿c軸方向可發現十六員環及八員環的隧洞，環的最大直徑約為10.344Å，在結構中的結晶水與扮演平衡電荷角色、經由質子化所形成的有機胺陽離子便分別填充於這十六員環及八員環的隧洞中。 Three new organically templated Metal Oxalatophosphates, (C4H16N3)[Fe2(C2O4)(HPO4)2(PO4)] (1)、(C4H14N2)[Ga2(C2O4)0.5(H2PO4)(PO4)2] ?2H2O (2)and (C4H16N3)0.5[Ga2(C2O4)0.5(H2PO4)0.5(PO4)2] ?1.5H2O(3),have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. Crystal data are as follows：compound 1, triclinic, P1 (No. 1), a = 6.3564(5) Å, b = 8.3201(7) Å, c = 9.2199(8) Å, α = 72.7970(10)°, β = 74.3560(10)°, γ = 70.2560(10)°, V = 430.52(6) Å3, Z = 1,and R1 = 0.0257;compound 2, triclinic, P-1 (No. 2), a = 8.0945(6) Å, b = 8.9585(7) Å, c = 13.2705(10) Å, α = 80.3780(10)°, β = 74.5750(10)°, γ = 77.9920(10)°, V = 900.94(12) Å3, Z = 1,and R1 = 0.0292; compound 3, monoclinic, C2/c (No. 1207) , a = 20.153(4) Å, b = 15.679(3) Å, c = 9.1070(18) Å, β = 105.92(3)°, V = 2767.3(9) Å3, Z = 8,and R1 = 0.0744.The structure of 1 consists of layers of FeO6 octahedra and phosphate tetrahedra,which are linked by oxalate group to generate a three-dimensional framework.The structure of 2 consists of anionic sheets of the formula [Ga2(C2O4)0.5(H2PO4)(PO4)2]2- with charge compensating diprotonated 1,4-Diaminobutanium cation and water molecules between the layers.The structure of 3 consists of dimers of GaO6 octahedra which are linked by oxalate group,conor-sharing GaO4 tetrahedra and phosphate tetrahedra to generate a three-dimensional framework. |
