鋅(II)與雙吡啶醯胺官能基組成之配位化合物的相轉變探討：陰離子效應

Phase Transformation of Zn(II)-Dipyridylamide-Based Coordination Frameworks : Anion Effects

葉建廷(Yeh, Chien Ting)

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(2012年)

摘要

我們使用N,N’-bis(pyridylcarbonyl)-4,4’-diaminodiphenyl thioether (paps) 、 N,N’-bis-(pyridylcarbonyl)-4,4’-diaminodiphenyl ether (papo) 及 N,N’-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (papc) 三種具有雙吡啶—醯胺官能基的配位基，分別與 Zn(PF6)2 和 Zn(BF4)2 合成一系列以二價鋅離子為中心的配位高分子。

依據所得配位高分子的晶體結構差異，我們將之分成下列三類：
(i) 一維雙鋸齒鏈（1D double zigzag, DZ）：{[Zn(paps)2 (H2O)2]•2PF6•2H2O}n (1), {[Zn(papo)2(H2O)2]•2PF6•2H2O}n (3) 及 {[Zn(papc)2(H2O)2]•2PF6•2CH3OH}n (5)
(ii) 二維聚環烷（2D polyrotaxane, PR）：[Zn(papo)2(PF6)2]n (4) 及 [Zn(papc)2(PF6)2]n (6)
(iii) 一維單鋸齒鏈：{[Zn(paps)(DMF)4]•2PF6•DMF}n (2)及{[Zn(papc)(DMSO)4]•2BF4•DMSO}n (7).
雖然所有化合物的二價鋅金屬中心均呈八面體的配位模式，但它們的晶體結構仍有所不同。鋅金屬的配位模式也分成三類，對 (i) 來說，是四個配位基上的吡啶官能基與兩個水分子配位；對 (ii) 來說，則是四個配位基上的吡啶官能基與兩個陰離子配位；對 (iii) 來說，是四個溶劑分子與兩個配位基上的吡啶官能基配位。

有趣的是，所有的鋸齒結構均具有相轉變的現象，也就是能藉由升溫使雙鋸齒結構轉變成聚環烷結構，反過來，也能藉由加水研磨使聚環烷結構回到雙鋸齒結構。我們透過單晶繞射的研究來了解這些化合物的晶體結構，並同時結合粉末繞射、熱重分析與熱差分析技術來研究不可逆向調控的相轉變性質。

關鍵字

配位高分子 ； 相轉換 ； 陰離子效應

並列摘要

We synthesized a series of ZnII-based coordination polymers by reacting each of three types 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) with Zn(PF6)2 as well as Zn(BF4)2.
Three different types of crystal structures of the coordination polymers obtained are classified as:
(i) 1D double zigzag (DZ): {[Zn(paps)2 (H2O)2]•2PF6•2H2O}n (1), {[Zn(papo)2(H2O)2]•2PF6•2H2O}n (3) and {[Zn(papc)2(H2O)2]•2PF6•2CH3OH}n (5).
(ii) 2D polyrotaxane (PR): [Zn(papo)2(PF6)2]n (4) and [Zn(papc)2(PF6)2]n (6).
(iii) 1D single zigzag: {[Zn(paps)(DMF)4]•2PF6•DMF}n (2) and {[Zn(papc)(DMSO)4]•2BF4•DMSO}n (7).
Although the octahedral coordination environment is observed for all ZnII metal centers, they differ in their crystal structures. The ZnII centre is coordinated by three types. For (i), there are four pyridines and two water molecules coordinated; for (ii), there are four pyridines and two anions coordinated; for (iii), there are four solvent molecules and two pyridines coordinated.
Interestingly, all zigzag-form complexes demonstrate the reversible phase transformation phenomena ie., from DZ form to PR by heating, and vise versa by grinding PR form with water. We have utilized single-crystal X-ray diffraction studies to solve the crystal structure. While the combination of PXRD, TGA and DSC techniques we studied the irreversibly switchable phase transformation properties.

並列關鍵字

Coordination Frameworks ； Phase Transfromation ； Anion Effect

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