以撓曲性配子設計有機金屬配位聚合物

Design of Metal-Organic Coordination Polymers with Flexible Ligands

李佩珊(Pei-Shan Lee)

指導教授 ： 曾添文

國立臺北科技大學/工程學院/化學工程研究所/碩士(2010年)

摘要

本論文第一部分是以撓曲性配子 4,4’-dipyridyl disulfide (4pds)與過渡金屬離子(Cu2+、Mn2+、Co2+、Zn2+) ，由室溫自組裝方式製備九個配位聚合物。經單晶X-ray繞射解析產物結構，得到三種結構，分別為二維雙互扣格子狀、一維鎖鏈狀、一維 zigzag chain 結構，並探討其各項物理性質。
本實驗之撓曲性配子 4,4’-dipyridyl disulfide (4pds)，在形成金屬配位聚合物時，可產生具鏡像異構物之特性，由於配子上 C-S-S-C 扭曲角度之不同，使所生成的化合物具不同堆疊方式，且藉此可調控所生成孔洞之大小，並借助所用溶劑之極性調控，使合成配位聚合物作客分子堆疊控制探討。
配位聚合物 1、2 為 CuCl2 與 4pds在室溫自組裝環境製備，同時得到藍色塊狀晶體及藍色針狀晶體產物，分別經單晶 X-ray 繞射解析，前者為二維雙互扣格子狀、後者為一維鎖鏈狀結構。
配位聚合物 3、4、5，為 CuCl2 與 4pds，在室溫自組裝的環境下製備而成，經單晶X-ray繞射解析產物，結構為一維鎖鏈狀結構，與化合物 2 為同分異構物。其結構藉配子本身芳香環的作用力，與溶劑甲醇、乙醇、丙醇、丁醇間的氫鍵作用力，進而使聚合時產生含不同客分子之化合物，並因藉由客分子的不同而調整結構內孔洞的大小及調整 C-S-S-C 之扭曲角度。
配位聚合物6、7、8 分別利用 Mn(NO3)2、Co(NO3)2 及 CoCl2 與 4pds 在室溫自組裝的環境下製備，經單晶 X-ray 繞射解析產物，皆得一維鎖鏈狀結構。
配位聚合物 9 為 Zn(NO3)2 與 4pds ，在室溫自組裝的環境下製備而成，經單晶 X-ray 繞射解析產物，結構為一維 zigzag chain 結構，其 4pds 有別於前者6-8，乃改採 M-form 的型式進行配位。
本論文第二部分，先合成含有Schiff base型式的配位基：4,4’-bis(3-pyridylmethyleneamine)-3,3’-dimethylbiphenyl（3-BPDBP）及 4,4’-bis-(4-pyridylmethyleneamine)-3,3'-dimethylbiphenyl（4-BPDBP）。利用室溫自組裝方式，Co(NO3)2與3-BPDBP 反應得到配位聚合物10。經單晶X-ray繞射解析其結構，發現化合物 10 之3-BPDBP以cisoid的形式與鈷金屬進行配位。以ZnCl2、ZnBr2 分別與 4-BPDBP依室溫自組法裝製備配位聚合物 11、12 。單晶X-ray繞射解析化合物 11 ，顯示其為一維zigzag chain，其4-BPDBP 以 transoid 的型式，與鋅金屬離子進行配位。
本研究詳細探討各化合物實驗合成方法、結構解析，並測量其熱穩定性，並對可彎曲基團之結構變化及構形差異，作深入探討。

關鍵字

自組裝 ； 配位聚合物 ； 結構分析 ； 撓曲性配子 4,4’-dipyridyl disulfide

並列摘要

The first part of this thesis is demonstrating the self-assembly of 4,4’-dipyridyl disulfide (4pds) ligand with flexible ribbon, with several transition metal ions (Cu2+, Mn2+, Co2+, Zn2+) to prepare nine coordination polymers under room temperature. Single-crystal X-ray structural analysis reveals that the structures of the polymers can be categorized into 2D structure with locked-helix-grid, 1D chain, and 1D zigzag chain, respectively.
It is interest that the metal coordination polymers with chiral can be obtained by using the flexible 4,4’-dipyridyl disulfide (4pds) as ligand. Furthermore, it could be finely tuned to study the diversity in architectures, the C-S-S-C torsion angles, and the pore sizes company with the entrapped guests within the synthesized compounds by controlling the polarity of solvents.
Compounds {[Cu(4pds)Cl2]∙1.5H2O}n (1) and {[Cu(4pds)2Cl2]∙H2O∙MeOH∙THF}n (2) were obtained by self-assembly reaction of 4pds and CuCl2 under room temperature. Single-crystal X-ray structural analysis reveals that the structure of compound 1 features a 2D locked-helix-grid MOFs and compound 2 exhibits a 1D chain.
{[Cu2(4pds)4Cl4]∙EtOH∙4H2O∙THF}n (3), {[Cu(4pds)2Cl2]∙2C3H7OH)}n (4) and {[Cu(4pds)2Cl2]∙2C4H9OH}n (5) were prepared by the self-assembly process in which CuCl2 is reacted with 4pds ligand under room-temperature. Single-crystal X-ray diffraction analysis revealed that compounds 3-5 are isomorphism and crystallized in the monoclinic space group P2/c, P2/c, and C2/c with 1D chain structure, respectively. Among them the π–π stacking interaction is found between the ligands. It is noteworthy the diversity of solvents, such as methanol, ethanol, propanol and butanol, which were found as the guests within the porosity of frameworks, and the corresponding torsion angles of C-S-S-C in these structures would be finely tuned. Compounds 6-8 were obtained by the self-assembly treatment of 4pds ligand with Mn(NO3)2, Co(NO3)2, and CoCl2, respectively, at room temperature. The structural analysis of compounds 6-8 reveals that all of them are 1D zigzag structure.
Compound [Zn(4pds)(NO3)2]n (9) was synthesized by reacting Zn(NO3)2 with 4pds, via self-assembly strategy at ambient temperature. An investigation of structural analysis reveals that compound 9 is a 1D zigzag structure, in which 4pds is coordinated to zinc metal atoms in M-form.
The second part of the thesis deals with the self-assembly reaction of Schiff-base ligands, 3-BPDBP and 4-BPDBP, with cobalt ions and zinc ions at room temperature to afford three MOFs 10-12 X-ray analysis reveals that the structure of compound {[Co(3-BPDBP)2(NO3)2]∙THF}n (10) is a 2D network, which is constructed by the treatment of Co(NO3)2 with 4,4’-bis(3-pyridylmethyleneamine)-3,3’-dimethylbiphenyl (3-BPDBP) ligand that is coordinated in specified cisoid form. Compounds [Zn(4-BPDBP)Br2]n (11) and [Zn(4-BPDBP)Cl2]n (12) were constructed by the reaction of ZnCl2 or ZnBr2 with 4,4’-bis(4-pyridylmethyleneamine)-3,3’-dimethylbiphenyl (4-BPDBP) and exhibit an one-dimensional zigzag chain character with transoid form.

並列關鍵字

Self-assembly ； supramolecule ； coordination polymer ； flexible ligands

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