含有機配位基之金屬磷酸鹽與金屬簇配位聚合物的合成、結構鑑定及性質研究

Synthesis, Structural Characterization and Properties of Metal Phosphates Incorporating Organic Ligands and Coordination Polymers Containing Polyoxometalates

張文中(Wen-Jung Chang)

指導教授 ： 張文中 ； 李光華

國立中央大學/理學院/化學系/博士(2008年)

摘要

本論文是利用中溫水熱法合成出15個具有新穎結構的含有機配位基之金屬磷酸鹽與金屬簇配位聚合物。按照金屬磷酸鹽與金屬簇的差異，將整個論文研究分成兩個系列。
第一個系列主要是利用2,2’-bpy以及1,10-phen當作有機配位基連結在中心金屬上，形成具有機配位基之金屬磷酸鹽，藉由中溫水熱法共得到了7個具有新穎結構的金屬磷酸鹽。受限於有機配位基鍵結模式，在第一個系列大都是一維或是二維結構；我們將這系列部分結論摘錄如下：(1) 加入HF形成A-1與A-2是反應過程所必須。(2) A-3與A-4則是藉由添加不同礦化劑所得到，同時也藉由固態核磁共振儀確認對稱氫原子。(3) 同樣藉由修改反應條件得到一組同份異構物A-5與A-6，在文獻中這樣的例子並不多見，同實例用磁性測量證實中心金屬價數。(4) 將磷酸改成苯磷酸成功得到A-7，同時利用固態核磁共振儀確Ga、P等原子的配位環境。
第二個系列則是利用金屬簇與金屬錯合物連結所形成的一系列化合物，共8個新穎結構，在這個系列共有3種不同金屬簇與金屬錯合物相互連結，結構型態相當多變。我們將這系列部分結論摘錄如下：(1) B-1、B-2以及B-3都是具有M[Mo6P4]2金屬簇的化合物，其中B-1為三維結構，B-2及B-3則是獨立金屬簇，利用磁性測量確認B-1的中心金屬價數。(2) B-4、B-5、B-6都具有[PMo12O40]3-，由結構中可發現這類型金屬簇可以當作陰離子或是進入結構中當作骨架，B-6具有新穎的金屬簇，利用固態核磁共振儀確P原子的配位環境；B-8則是單取代[PMo12O40]3-的一個新穎化合物，同時利用熱重分析儀發現化合物有回水現象。(3) B-7則是以[P2Mo5O23]6-金屬簇當作柱體，金屬錯合物則是形成配位網狀結構，兩者相互連結形成三維結構。

關鍵字

金屬簇配位聚合物 ； 水熱法 ； 金屬磷酸鹽

並列摘要

In this thesis, we focus on two areas: 1) synthesis, structural characterization of metal phosphates incorporating organic ligands; and 2) synthesis, structural characterization of coordination polymers containing polyoxometalates. In the first area, we plan to use 2,2’-bipyridine or 1,10-phenathroline to synthesize a new organic-inorganic hybrid compound. Most of these compounds contain neutral frameworks without organic amine templates. Metal phosphates containing organic components coordinated directly to metal atoms are scarce, as compared with the large number of metal phosphate in literature where the organic components mostly occur as charge compensating and space-filling constituents. We already have synthesized 7 compounds with novel structures, we excerpt some conclusions as following: (a) It appears that the addition of HF to the reaction mixture is important to the formation of A-1 and A-2, (b) It appears that the addition of LiBO2 to the reaction mixture is important to the formation of A-3H and HF facilitates the crystal growth, (c) Two polymorphs (A-5 and A-6) of an organic-inorganic hybrid compound have been synthesized by hydrothermal reactions. The synthesis has many parameters and a subtle change in the reaction conditions can greatly affect the course of the reactions. It appears that the addition of TEABr to the reaction mixture is important to the formation of A-5, and (d) all compounds consist of similar secondary building units which are extend into 3D supramolecular arrays via hydrogen bond and π-π stacking interactions of 2,2’-bpy or 1,10-phen ligands.
In the second area, we are interested in coordination polymers containing polyoxometalates. We already have synthesized 8 compounds with novel structures, we excerpt some conclusions as following: (a) although a good number of compounds containing anionic M[Mo6P4]2 dimers connected by transition metal complexes have been reported, B-1 is the first example of extended framework solid containing the polyoxomolybdophosphate clusters interconnected by both transition metal complexes and organic moieties, (b) B-4 represents the first example of molybdenum-oxide-based organic-inorganic hybrid frameworks templated by double Keggin anions. With hindsight, we can imagine that more new metal-oxide-based hybrid materials could be prepared by replacement of organic-manganese complex segments and/or by selection of different Keggin anion or other polyanion templates, (c) for B-5 and B-6, there is no doubt that the nature of the secondary transition metal ion, Cu(II), has a key role in the formation of these novel structures because of its capacity to adopt various coordination environments and the Jahn-Teller effect which allows an elongation of the axial Cu-O and Cu-Cl distances, (d) the 3D structure, B-7, based on a transition-metal coordination polymer sheet linked by Strandberg clusters, and (e) a new derivative of polyoxometalate, B-8, with a pendant organic ligand, which represents a rare organic capped-structure containing Keggin polyanion.

並列關鍵字

clusters ； coordination polymer ； metal phosphates ； hydrothermal synthesis

參考文獻

2. Batten, S. R.; Robson, R. Angew. Chem. Int. Ed. 1998, 37, 1460 and references therein.

3. Davis, M. D. Nature 2002, 417, 813.

5. Rao, C. N. R.; Natarajan, S.; Vaidhyanathan, R. Angew. Chem. Int. Ed. 2004, 43, 1466 and references therein.

6. Batten, S. R.; Robson, R. Angew. Chem. Int. Ed. 1998, 37, 1460 and references therein.

8. Yang, W.; Lu, C. Inorg. Chem. 2002, 41, 5638.