含吡啶環可撓性配子之銅、銀金屬配位聚合物：自組裝合成、結構鑑定與性質研究
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2016
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本論文探討含四吡啶環之可撓性配子1,4-bis(di-(3-picolyl)aminomethyl)benzene (p-bpab)與銅離子或銀離子之自組裝反應，並研究生成之配位聚合物的結構特性及其性質。
第一部分為有機配子p-bpab搭配具羧酸基之有機配子與氯化銅水溶液於攝氏120 ℃下進行水熱反應，得到三種化合物{[Cu4(p-bpab)2(suc)3Cl2]•(H2O)6}n (1)、[Cu2(p-bpab)(1,4-ndc)2(H2O)2]n (2)以及{[Cu2(p-bpab)(1,4-ndc)2(H2O)2]•(naphthalene)3}n (3)。化合物1、2與 3的結構都是銅離子與具羧酸基之有機配子形成一維鏈狀結構，並以可撓曲配子p-bpab與一維鏈狀結構上之銅離子配位，形成二維或三維結構。其中化合物1由銅離子、p-bpab與succinic acid鍵結形成特殊三維結構。化合物2由銅離子、p-bpab與nap-1,4-dicarboxylic acid組裝形成二維結構。化合物3之合成條件與化合物2相近，但多加萘進行反應，發現萘環與p-bpab上之吡啶環藉由ππ作用力而導致化合物3之整體二維結構與化合物2截然不同。
第二部分為銀離子與可撓曲配子p-bpab進行室溫自組裝合成，因銀鹽不同陰離子之影響，而得到三種不同的化合物{[Ag2(p-bpab)]•(NO3)2•(CH3OH)}n (4)、{[Ag2(p-bpab)]•(SbF6)2•(CH3OH)6}n (5)及{[Ag2(p-bpab)]•(NO3)•(BF4)•(CH3OH)}n (6)，並探討陰離子效應對整體結構影響。使用硝酸銀與p-bpab反應形成具一維正弦波狀結構的化合物4，使用六氟銻酸銀與p-bpab反應形成具一維鋸齒狀結構化合物5，不同陰離子造成的模板效應以及氫鍵等作用力而導致不同的結構。若將化合物4的配方多加入四氟硼酸鈉，反應後形成的化合物6則為化合物4結構中一個硝酸根離子被置換成四氟硼酸陰離子，但化合物6依然為一維正弦波狀結構，且與化合物4大同小異。本結果顯示具硝酸根離子之一維正弦波狀結構非常穩定，即使加入其他陰離子也不影響其結構變化。
第三部分為硝酸銀與p-bpab之室溫自組裝合成，再加入不同芳香環溶劑反應，得到兩種化合物{[Ag2(p-bpab)]•(NO3)2•(toluene)}n (7)、{[Ag8(p-bpab)4]•(NO3)8•(pyrene)•(THF)2}n (8)，並探討客分子效應對整體結構影響。研究發現即使加入能與有機配子p-bpab上的芳香環形成作用力的溶劑如甲苯以及芘，化合物7以及化合物8兩者結構皆為一維正弦波狀結構，且與化合物4之結構大同小異，顯示加入少許芳香環溶劑不足以影響結構變化。
第四部分探討化合物4是否具有吸附甲苯的能力，並產生類似於化合物7的結構。結果顯示化合物4可能具有吸附甲苯的能力，但於室溫下的吸附量有限，因此無法完全轉換成類似化合物7的結構。
In this thesis, a flexible pyridine ligand 1,4-bis(di-(3-picolyl)aminomethyl)benzene (p-bpab) was synthesized and characterized. We first treated CuCl2 with the p-bpab ligand and several carboxylic acid based ligands under hydrothermal conditions to afford a series of coordination polymers {[Cu4(p-bpab)2(suc)3Cl2]•(H2O)6}n (1), [Cu2(p-bpab)(1,4-ndc)2(H2O)2]n (2) and {[Cu2(p-bpab)(1,4-ndc)2(H2O)2]•(naphthalene)3}n (3). All of these compounds (13) are comprised of one-dimensional (1D) linear chains, composed of carboxylate ligands and Cu(II) metal ions. These 1D linear structures are linked with each other via the p-bpab ligand. The linkage of 1D linear chains in compound 1 results in the formation of a 3D crystal structure, as the p-bpab ligand adopts a different degree of distortion. However, the 1D linear chains in compound 2 which composed of 1,4-nap-dicarboxylate and Cu(II) ions, can be transformed into a 2D structure with the support of the p-bpab ligand. When naphthalene is added to compound 2, a new crystal structure 3 is formed, where naphthalene acts as a guest molecule. In the next stage of research, the p-bpab ligand was further utalized to react with Ag(I) ions with different counteranions by means of a solvent diffusion method at room temperature. A series of Ag-based coordination compounds {[Ag2(p-bpab)]•(NO3)2•(CH3OH)}n (4), {[Ag2(p-bpab)]•(SbF6)2•(CH3OH)6}n (5) and {[Ag2(p-bpab)]•(NO3)•(BF4)•(CH3OH)}n (6) were prepared, and effects of counteranions in these compounds were studied. All of these compound adopted 1D crystal structures. However, significant structural changes were observed between a 1D sinusoidal structure in compound 4 and a 1D zigzag structure in compound 5. The results clearly show that different counteranions can have different effects in crystal structure, including changes in the template effect and hydrogen bonding. In compound 4, when one nitrate counteranion is replaced by tetrafluorate, a similar 1D sinusoidal structure 6 is formed, indicating that a 1D sinusoidal structure 4 with a nitrate counteranion inside structure is a very stable arrangement and will not change when one nitrate counteranion in a 1D sinusoidal structure is replaced with another counteranion (BF4). The p-bpab ligand and silver(I) nitrate salts were used with different guest molecules such as toluene and pyrene to synthesize coordination polymers by a solvent diffusion method at room temperature. Compounds {[Ag2(p-bpab)]•(NO3)2•(toluene)}n (7), {[Ag8(p-bpab)4]•(NO3)8•(pyrene)•(THF)2}n (8) were synthesized and the effects of different guest molecules were studied. All of these compounds show 1D sinusoidal structures that are similar to compound 4. The guest molecules trapped in the 1D structure layers of compound 4 could replaced by toluene, pyrene and THF, indicating that the crystal structure of compound 4 remains very stable after the exchange of some guest molecules. In addition, the ability of compound 4 to absorb toluene molecule was studied, and results show that compound 4 has only a limited ability to absorb toluene molecules.
In this thesis, a flexible pyridine ligand 1,4-bis(di-(3-picolyl)aminomethyl)benzene (p-bpab) was synthesized and characterized. We first treated CuCl2 with the p-bpab ligand and several carboxylic acid based ligands under hydrothermal conditions to afford a series of coordination polymers {[Cu4(p-bpab)2(suc)3Cl2]•(H2O)6}n (1), [Cu2(p-bpab)(1,4-ndc)2(H2O)2]n (2) and {[Cu2(p-bpab)(1,4-ndc)2(H2O)2]•(naphthalene)3}n (3). All of these compounds (13) are comprised of one-dimensional (1D) linear chains, composed of carboxylate ligands and Cu(II) metal ions. These 1D linear structures are linked with each other via the p-bpab ligand. The linkage of 1D linear chains in compound 1 results in the formation of a 3D crystal structure, as the p-bpab ligand adopts a different degree of distortion. However, the 1D linear chains in compound 2 which composed of 1,4-nap-dicarboxylate and Cu(II) ions, can be transformed into a 2D structure with the support of the p-bpab ligand. When naphthalene is added to compound 2, a new crystal structure 3 is formed, where naphthalene acts as a guest molecule. In the next stage of research, the p-bpab ligand was further utalized to react with Ag(I) ions with different counteranions by means of a solvent diffusion method at room temperature. A series of Ag-based coordination compounds {[Ag2(p-bpab)]•(NO3)2•(CH3OH)}n (4), {[Ag2(p-bpab)]•(SbF6)2•(CH3OH)6}n (5) and {[Ag2(p-bpab)]•(NO3)•(BF4)•(CH3OH)}n (6) were prepared, and effects of counteranions in these compounds were studied. All of these compound adopted 1D crystal structures. However, significant structural changes were observed between a 1D sinusoidal structure in compound 4 and a 1D zigzag structure in compound 5. The results clearly show that different counteranions can have different effects in crystal structure, including changes in the template effect and hydrogen bonding. In compound 4, when one nitrate counteranion is replaced by tetrafluorate, a similar 1D sinusoidal structure 6 is formed, indicating that a 1D sinusoidal structure 4 with a nitrate counteranion inside structure is a very stable arrangement and will not change when one nitrate counteranion in a 1D sinusoidal structure is replaced with another counteranion (BF4). The p-bpab ligand and silver(I) nitrate salts were used with different guest molecules such as toluene and pyrene to synthesize coordination polymers by a solvent diffusion method at room temperature. Compounds {[Ag2(p-bpab)]•(NO3)2•(toluene)}n (7), {[Ag8(p-bpab)4]•(NO3)8•(pyrene)•(THF)2}n (8) were synthesized and the effects of different guest molecules were studied. All of these compounds show 1D sinusoidal structures that are similar to compound 4. The guest molecules trapped in the 1D structure layers of compound 4 could replaced by toluene, pyrene and THF, indicating that the crystal structure of compound 4 remains very stable after the exchange of some guest molecules. In addition, the ability of compound 4 to absorb toluene molecule was studied, and results show that compound 4 has only a limited ability to absorb toluene molecules.
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超分子化學, 配位聚合物, 自組裝, 陰離子效應, Supramolecular chemistry, Coordination polymer, Self-assembly, Anion effect