含柔性雙醯胺雙吡啶與四芽羧酸基的配位高分子晶體工程

本論文分五部份探討含柔性雙醯胺雙吡啶與四芽羧酸基配位高分子的合成，結構與特性。第一部分：此部份回顧了本實驗室在過去幾年在柔性雙醯胺雙吡啶的研究工作。這種配位基具有柔軟的-CH2-骨架與多樣性的鍵結模式，可經由氮原子或氧原子鍵結到金屬原子上，在合成配位高分子上具有重大的效益。我們將回顧以此配位基或加入羧酸配位基所合成的配位高分子的結構並探討此類配位基在配位高分子中的構型。第二部分: 此部分報導了兩對的超分子異構物:[HgBr2(GAG-L1)]∞ [L1 = N,N-di(3-pyridyl)adipoamide] ， 1 ，[HgBr2(AAA-L1)]∞， 2 ， [HgI2(GAG-L1)]∞， 3 ，與 [HgI2(AAA-L1)]∞， 4。這四化合物以不同的方法製備，並以單晶繞射儀鑑定其結構。化合物1形成一個meso-helical的鏈狀化合物，化合物2與4為一維的螺旋狀化合物，而化合物3為sinusoidal鍊狀化合物。化合物1與3的L1配位機具有GAG trans syn-syn的構型，而在化合物2與4中具有AAA trans syn-syn的構型。化合物1與3在加熱或水熱的條件下可可逆地轉換為2與4。除此之外化合物1在固態中呈現較強的藍紫色的螢光，化合物2與3的藍綠螢光較弱，而化合物4偵測不到螢光。第三部分:利用柔性配位基bis(3,5-dicarboxyphenyl)adipoamide， H4L6， bis(N-pyrid-3-ylmethyl)adipoamide， L4 與 bis(N-pyrid-3-ylmethyl) suberoamide， L5，在水熱條件下可製備四個配位高分子{[M(L6)0.5(L4)(H2O)2]H2O}n (M = Co, 5; Ni, 6) 與{[M2(L6)(L5)2(H2O)4]3H2O}n (M = Co, 7; Ni, 8)。這些化合物的結構皆以單晶繞射儀鑑定。化合物5 - 8具有相同的拓譜學結構，皆屬2-fold交互穿透的三維結構，拓譜學名稱為moganite。除此之外，兩個Co(II)化合物在加熱去除溶劑後具變色的特性，且可進行可逆的轉換，但Ni(II)化合物不具此特性。此四化合物皆具良好的光降解能力，且Co(II)化合物效率較Ni(II)化合物為佳。第四部分:利用柔軟的四芽羧酸bis(3,5-dicarboxyphenyl) adipoamide， H4L6 與其異構物，bis(2,5-dicarboxyphenyl)adipoamide ，H4L7，以水熱法製備了三個Mg(II)配位高分子[Mg2(L6)(H2O)2]2EtOH3H2O， 9 ，[Mg2(L6)(H2O)8] ， 10與 [Mg2(L7)(H2O)6]H2O， 11。其結構以單晶繞射儀鑑定。化合物9與10的形成與溶劑比例有關且皆為穩定的產物。化合物9的配位基形成獨特的8-nonadentate構型，為三維的結構，其拓譜學為(44.66)-pcu-5-Pmna，而化合物10與11的配位基分別形成4-tetradentate 與 6-hexadentate構型，其結構分別為一維鍊狀與具{4.62}2{42.610.83}-rtl拓譜學的三維結構。化合物9與10可進行一系列的可逆結構轉換，但化合物11的結構轉換則為不可逆。所有的化合物皆發生藍色的螢光，其中化合物11的強度較佳。第五部分:利用三個柔軟的配位基bis(3,5-dicarboxyphenyl) adipoamide ，H4L6，N,N’-bis(3-pyridyl)sebacoamide，L2 與N,N’-bis(3-pyridyl)dodecanedipoamide， L3，以水熱法製備了四個配位高分子[Co(L6)0.5(H2O)3]H2O， 12， [Co(L6)0.5(L2)(H2O)]4H2O， 13， [Cd(L6)(H2O)2]2EtOH3H2O ，14 與 [HgI2(L3)]∞, 15。這些化合物的結構皆以單晶繞射儀鑑定。化合物12形成二維的環狀結構，其拓譜學為(4.62)2(42.62.82)，化合物13為二維結構，其拓譜學為{42.82.102}{42.84}2{4}2，化合物14為三維之結構，其拓譜學為(44.66)-pcu，而化合物15為一維的鏈狀結構。化合物12與13的熱分析亦將加以探討。

關鍵字

雙醯胺雙吡啶基

並列摘要

In this dissertation, the syntheses, structures and properties of coordination polymers based on the flexible bis-pyridyl-bis-amide and/or tetracarboxylate ligands, have been extensively discussed and summarized basically in five parts. Part I: The contribution of flexible bis-pyridyl-bis-amide (bpba) ligands, which are also known as versatile ligands possessing various active coordination atoms (N and O) and different flexible –CH2– skeletons, is significant in the construction of coordination polymers. In this Highlight, structures of the different dimensional networks based on the flexible bpba ligands with or without participation of auxiliary polycarboxylate ligands are discussed, along with an overview of the preparations and conformations of the ligands. Part II: Two pairs of Hg(II) supramolecular isomers, [HgBr2(GAG-L1)]∞ [L1 = N,N-di(3-pyridyl)adipoamide], 1, and [HgBr2(AAA-L1)]∞, 2, and [HgI2(GAG-L1)]∞, 3, and [HgI2(AAA-L1)]∞, 4, have been successfully synthesized by various methods, and structurally characterized by single crystal X-ray crystallography. Complex 1 forms a one-dimensional (1D) meso-helical chain, 2 and 4 exhibit normal 1D helical chains, while 3 displays a 1D sinusoidal chain. The L1 ligands in 1 and 3 display GAG trans syn-syn conformation, while those in 2 and 4 adopt the AAA trans syn-syn conformation. In addition, complexes 1 and 3 can be irreversibly transformed to 2 and 4, respectively, under simple heating or hydrothermal condition. Moreover, complex 1 exhibits intense violet-blue photoluminescence in the solid state, whereas 2 and 3 display weak broad emissions in the blue-green region and 4 shows undetectable emission intensity. Part III: By utilizing the flexible ligands, bis(3,5-dicarboxyphenyl)adipoamide, H4L6; bis(N-pyrid-3-ylmethyl)adipoamide, L4; and bis(N-pyrid-3-ylmethyl) suberoamide, L5, four coordination polymers of the types {[M(L6)0.5(L4)(H2O)2]H2O}n (M = Co, 5; Ni, 6) and {[M2(L6)(L5)2(H2O)4]3H2O}n (M = Co, 7; Ni, 8) have been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Complexes 5 - 8 are topologically identical coordination polymers having the moganite type 2-fold interpenetrating 4,4-connected 3D net. Additionally, both Co(II) complexes are thermochromic and exhibit the reversible structural transformation on dehydration/rehydration followed by the color change but Ni(II) complexes are unable to show such behavior. All four complexes display good photo-degradation performance and the Co(II) complexes show slightly higher efficiencies than the Ni(II) ones. Part IV: By using a new flexible tetracarboxylic acid, bis(3,5-dicarboxyphenyl) adipoamide, H4L6, and its isomer, bis(2,5-dicarboxyphenyl)adipoamide, H4L7, three Mg(II) coordination polymers, [Mg2(L6)(H2O)2]2EtOH3H2O, 9, [Mg2(L6)(H2O)8], 10, and [Mg2(L7)(H2O)6].H2O, 11, have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Complexes 9 and 10 are the solvent ratio dependent hydrothermally stable products. The tetracarboxylate ligand of complex 9 adopts a unique 8-nonadentate bonding mode, resulting in a three-dimensional (3D) 5-connected uninodal (44.66)-pcu-5-Pmna net, whereas those of 10 and 11 display the 4-tetradentate and 6-hexadentate bonding modes, forming a 1D linear chain and a 3,6-connected 2-nodal 3D net having {4.62}2{42.610.83}-rtl topology, respectively. Complex 9 shows a series of structural transformations on heating up to 200 oC and almost reversible structural transformation when the activated products were immersed in the mixture of ethanol and water or on hydrothermal. Likewise, complex 10 exhibits reversible structural transformation on heating/hydrothermal while 11 exhibits the irreversible structural transformations. All three complexes exhibit blue light emissions and that of complex 11 is much more intense. Part V: By applying three flexible ligands, bis(3,5-dicarboxyphenyl) adipoamide, H4L6; N,N’-bis(3-pyridyl)sebacoamide, L2 and N,N’-bis(3-pyridyl)dodecanedipoamide, L3; four new coordination polymers: [Co(L6)0.5(H2O)3]H2O, 12; [Co(L6)0.5(L2)(H2O)]4H2O, 13; [Cd(L6)(H2O)2]2EtOH3H2O, 14 and [HgI2(L3)]∞, 15; have been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Complex 12 forms the 2D looped like structure with (4.62)2(42.62.82) topology, while 13 possesses a 2,4,4-connected-3-nodal 2D net with the new topology {42.82.102}{42.84}2{4}2. Further, complex 14 possesses a three-dimensional (3D) 5-connected uninodal (44.66)-pcu net, whereas 15 displays a 1D linear chain. Moreover, the thermal properties of complexes 12-13 were investigated.

並列關鍵字

Bis-pyridyl-bis-amide Ligands

參考文獻

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含柔性雙醯胺雙吡啶與四芽羧酸基的配位高分子晶體工程

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