雙吡啶醯胺官能基組成之配位化合物的相轉變探討：金屬效應

Phase Transformation of Dipyridylamide-Based Coordination Frameworks : Metal Effects

蔡妙昕(Miao-Hsin Tsai)

指導教授 ： 曾炳墝

國立中正大學/理學院/化學暨生物化學系/碩士(2013年)

摘要

本篇論文主要利用一系列具有雙醯官能基的配位基N,N'-bis(pyridylcarbonly)-4,4'-diphenyl thioether (paps)、N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenylether (papo)和N,N’-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (papc)，成功的與鈷(II)、鎳(II)、銅(II)進行自組裝合成，得到一維雙鋸齒狀 (double-zigzag, DZ) 結構的{[Co(paps)2(H2O)2](ClO4)2(H2O)2}n (1)、{[Co(papo)2(H2O)2](ClO4)2(H2O)2}n (2)、{[Co(papc)2(H2O)2](ClO4)2(H2O)2(C7H8)}n (3)、{[Ni(paps)2(H2O)2](ClO4)2(H2O)2}n (4)、{[Ni(papo)2(H2O)2](ClO4)2(H2O)2}n (5)，以及二維聚輪烷 (polyrotaxane, PR) 骨架的[Cu(paps)2(ClO4)2] (6)。而兩者結構的差異源自於金屬中心在軸位上配位水分子抑或過氯酸根陰離子。另外，雖然[Cu(papo)2(ClO4)2] (7) 和[Cu(papc)2(ClO4)2] (8) 無法順利的得到其單晶結構，但是仍能以粉末繞射鑑定之。
其中，1、2、4、5都可以經由升溫導致結構由一維雙鋸齒狀結構轉換至二維聚輪烷骨架。而同時可以藉由加水研磨的方式，由二維聚輪烷骨架轉換至一維雙鋸齒狀結構，形成一個可逆的循環。但是，3、6、7和8無法形成可逆的轉換，化合物3可能是晶格內堆疊模式所導致相轉換行為的改變。也相對證明類似的配位基但是結構內間隔基 (S、O和CH2) 不同而導致在自組裝後造成明顯的效應。除此之外，6-8經由加水研磨之後亦無法由一維雙鋸齒狀結構轉換至二維聚輪烷骨架，此結果和實驗室先前的研究工作比較，可說明當置換中心金屬離子為銅(II)時，會對相轉換行為造成顯著的影響。然而，鈷(II)和鎳(II)與之前鋅(II)的化合物有著一致的性質，此差異性有可能與銅(II)的楊-泰勒效應 (Jahn-Teller effect) 有關。

關鍵字

相轉變 ； 配位高分子 ； 金屬效應

並列摘要

We used a series of dipyridylamide ligands, N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl thioether (paps)、 N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl ether (papo) and N,N’-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (papc), to react with Co(II)、Ni(II) and Cu(II) respectively to give one-dimensional double-zigzag (DZ) frameworks, {[Co(paps)2(H2O)2](ClO4)2(H2O)2}n (1)、{[Co(papo)2(H2O)2](ClO4)2(H2O)2}n (2)、{[Co(papc)2(H2O)2](ClO4)2(H2O)2(C7H8)}n (3)、{[Ni(paps)2(H2O)2](ClO4)2(H2O)2}n (4)、{[Ni(papo)2(H2O)2](ClO4)2(H2O)2}n (5), and two-dimensional polyrotaxane (PR) frameworks, [Cu(paps)2(ClO4)2] (6), in the different reaction conditions. This difference relies on the fact that water coordinates to the center ion in double-zigzag frameworks , but anions coordination is found in polyrotaxane frameworks. Although [Cu(papo)2(ClO4)2] (7) and [Cu(papc)2(ClO4)2] (8) can not get its crystal structure successfully, but still can identify by powder X-ray diffraction.
Interestingly, 1, 2, 4 and 5 were demonstrated to show phase transformation properties from double-zigzag frameworks to polyrotaxane frameworks by heating and grinding in the presence of moisture, and such a structural transformation can also be proven experimentally by powder X-ray diffraction studies. However, 3, 6, 7 and 8 cannot perform such a reversible cycle. Compound 3 is due to the steric effect of papc as the related to Zn(II) complexes. By replacing the above metal ions with Cu(II), the irreversible phase transformation has been observed, and thus is most likely ascribed to the Jahn-Teller effect of Cu(II).

並列關鍵字

Phase Transitions ； Coordination Frameworks ； Metal Effects

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