雙吡啶醯胺官能基組成之配位化合物的相轉變探討：銅(II)離子效應

Phase Transformation of Dipyridylamide-Based Coordination Frameworks :A Cu(II) Effect

林煜庭(Yu-Ting Lin)

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(2015年)

摘要

本篇論文研究主要以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)為配位基，各別與過氯酸銅(II)進行合成，得到配位高分子[Cu(papo)2(ClO4)2]n (1)、{[Cu(papo)2(H2O)2](ClO4)2}n (2)、{[Cu(paps)2(H2O)2](ClO4)2}n (3)和[Cu(papc)2(ClO4)2]n (4)。1-4可經由X-光單晶繞射解析確定其固態結構，其中1、4為二維聚輪烷(polyrotaxane, PR)結構，而2、3為一維雙鋸齒狀(double-zigzag, DZ)結構。1、4的銅(II)金屬中心以六配位形式存在，並且配位四個來自配位基上的氮原子及兩個來至過氯酸根的氧，而2、3則沒有配位過氯酸根的存在，取而代之的是兩個水分子。銅(II)金屬為d9電子組態有Jahn-Teller distortion現象，造成軸位鍵長會較平面鍵長還要長，例如化合物1中軸位鍵長約2.5 Å而平面鍵長約2.0 Å。

將化合物1、4加水研磨與長時間泡水後之粉末繞射圖譜發現無法從聚輪烷結構(PR)改變至雙鋸齒狀結構(DZ)，和實驗室先前的鋅(II)系統研究比較，可發現當鋅(II)金屬離子置換成銅(II)金屬離子時，會對相轉換行為造成顯著的影響。將化合物2、3做變溫粉末繞射實驗，可發現原本雙鋸齒狀結構(DZ)可經由加熱轉變為聚輪烷結構(PR)，兩結構間為不可逆相轉變行為。造成這不可逆的結果推測是二價銅離子本身有楊-泰勒效應(Jahn-Teller effect)。

關鍵字

雙吡啶醯胺官能基組成之配位化合物的相轉變探討：銅(II)離子效應

並列摘要

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), were used to react with Cu(ClO4)2 to give four coordination polymers [Cu(papo)2(ClO4)2]n (1)、{[Cu(papo)2(H2O)2](ClO4)2}n (2)、{[Cu(paps)2(H2O)2](ClO4)2}n (3), and [Cu(papc)2(ClO4)2]n (4), respectively. All crystal structures of 1 - 4 have been determined by X-ray diffraction, indicating that 1, 4 are two-dimensional polyrotaxane (PR) frameworks and 2, 3 are one-dimensional double-zigzag (DZ) ones. This difference relies on the fact that water coordinates to the Cu(II) ion in double-zigzag frameworks, but instead anion coordination is found in polyrotaxane frameworks.

In fact, 1 and 4 do not show phase transformation from polyrotaxane frameworks to double-zigzag ones by grinding in the presence of moisture or soaked in the water. However, 2 and 3 did show phase transformation from double-zigzag frameworks to polyrotaxane ones by heating. It is noted that by replacing the previous Zn(II) ions with Cu(II), the irreversible phase transformation for 1 and 4 has been observed, and thus is most likely ascribed to the Jahn-Teller effect of Cu(II).

並列關鍵字

Phase Transformation of Dipyridylamide-Based Coordination Frameworks :A Cu(II) Effect

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