含雙醯胺雙吡啶與掌型雙羧酸配位基配位高分子的合成、結構與催化性質研究

Syntheses, Structures and Catalytic Properties of Coordination Polymers Based on Bis-pyridyl-bis-amide and Chiral Dicarboxylate Ligands

鄭永塘(Yung-Tang Cheng)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2019年)

https://doi.org/10.6840/cycu201900339

摘要

本篇論文藉由掌型與非掌型雙羧酸配位基與不同長度的雙醯胺雙吡啶配位基 N,N'-di(3-pyridyl)adipoamide (L1)、N,N'-di(3-pyridyl)sebacoamide (L2)、N,N'-di(3-pyridyl)ethanediamide (L3)與N,N'-di-3-pyridinyl-[1,1'-Biphenyl]-4,4'-dicarboxamide (L4)，搭配數種二價過渡金屬鹽類以水熱法的方式合成出19種化合物: {[Zn(4,4'-bipy)(L-DBTA)(H2O)2]∙H2O}n (L-H2DBTA = (−)-dibenzoyl-L-tartaric acid; 4,4'-bipy = 4.4'-bipyridine), 1, {[Zn(4,4'-bipy)(D-DBTA)(H2O)2]∙H2O}n (D-H2DBTA = (+)-dibenzoyl-D-tartaric acid), 2, {[Zn(L1)(L-DBTA)]∙H2O}n, 3, {[Zn(L1)(D-DBTA)]∙H2O}n, 4, {[Cu(L1)(L-DBTA)]∙H2O}n, 5, {[Cu(L1)(D-DBTA)]∙H2O}n, 6, {[Co(L1)(L-DBTA)(H2O)2]}n, 7, {[Co(L1)(D-DBTA)(H2O)2]}n, 8, [Cd(L1)(L-DBTA)]n, 9, [Cd(L1)(D-DBTA)]n, 10, {[Co(L2)(L-DBTA)]∙H2O}n, 11, {[Co(L2)(D-DBTA)]∙H2O}n, 12, {[Zn(L2)(L-DBTA)]∙2H2O}n, 13, {[Cd(L2)(L-DBTA)(EtOH)]∙H2O}n, 14, {[Zn(L3)(L-DBTA)]∙6H2O}n, 15, {[Zn(1,4-BDC)(L4)]∙2H2O}n (1,4-H2BDC = terephthalic acid), 16, {[Zn(1,3-BDC)(L4)]．H2O}n (1,3-H2BDC = isophthalic acid), 17, [Cd(2-BDCBA)(DMF)(H2O)]n {2-H2BDCBA = 2,2'-[[1,1'-biphenyl]-4,4'-diylbis(carbonylimino)]bis-benzoic acid}, 18, {[Cd2(2-BDCBA)2(4,4'-bipy)1.5(H2O)]∙H2O∙DMF}n, 19, 以上化合物皆藉由X-ray 繞射儀鑑定其結構，並以粉末X-ray繞射儀與熱重分析儀來研究化合物的特性。
化合物1 - 6、9、10與17具有sql拓譜學的二維結構。化合物7、8與16具有dia拓譜學之三維結構與3-fold相互貫穿。化合物11、12與13具有dmp拓譜學之三維結構。化合物14具有4L2拓譜學之二維結構。化合物15具有neb拓譜學之三維結構。化合物18具有一維的凹凸鏈狀結構。化合物19具有3,4,5-L16拓譜學之二維結構。本文亦探討部分化合物的發光與斯特雷克反應催化特性。

關鍵字

配位高分子 ； 雙醯胺雙吡啶 ； 催化性質

並列摘要

A series of chiral coordination polymers constructed from N,N'-di(3-pyridyl)adipamide (L1), N,N'-di(3-pyridyl)sebacoamide (L2), N,N'-di(3-pyridyl)ethanediamide (L3) and N,N'-di-3-pyridinyl-[1,1'-Biphenyl]-4,4'-dicarboxamide (L4) and chiral and achiral dicarboxylic acid ligands, including {[Zn(4,4'-bipy)(L-DBTA)(H2O)2]∙H2O}n (L-H2DBTA = (−)-dibenzoyl-L-tartaric acid), 1, {[Zn(4,4'-bipy)(D-DBTA)(H2O)2]．H2O}n (D-H2DBTA = (+)-dibenzoyl-D-tartaric acid), 2, {[Zn(L1)(L-DBTA)]∙H2O}n, 3, {[Zn(L1)(D-DBTA)]∙H2O}n, 4, {[Cu(L1)(L-DBTA)]∙H2O} n, 5, {[Cu(L1)(D-DBTA)]∙H2O} n, 6, {[Co(L1)(L-DBTA)(H2O)2]}n, 7, {[Co(L1)(D-DBTA)(H2O)2]}n, 8, [Cd(L1)(L-DBTA)]n, 9, [Cd(L1)(D-DBTA)]n, 10, {[Co(L2)(L-DBTA)]∙H2O}n, 11, {[Co(L2)(D-DBTA)]∙H2O}n, 12, {[Zn(L2)(L-DBTA)]∙2H2O}n, 13, {[Cd(L2)(L-DBTA)(EtOH)]∙H2O}n, 14, {[Zn(L3)(L-DBTA)]∙6H2O}n, 15, {[Zn(1,4-BDC)(L4)]∙2H2O}n (1,4-H2BDC = terephthalic acid), 16, {[Zn(1,3-BDC)(L4)]∙H2O}n (1,3-H2BDC = isophthalic acid), 17, [Cd(2-BDCBA)(DMF)(H2O)]n {2-H2BDCBA = 2,2'-[[1,1'-biphenyl]-4,4'-diylbis(carbonylimino)]bis-benzoic acid}, 18, {[Cd2(2-BDCBA)2(4,4'-Bipy)1.5(H2O)]∙H2O∙DMF}n 19, have been synthesized by using hydrothermal reactions. Their structures have been determined by single-crystal X-ray diffraction analyses and characterized by powder X-ray diffraction and thermal gravimetric analysis.
Complexes 1 – 6, 9, 10 and 17 are 2D layers with the sql topology, while complexes 7, 8 and 16 display 3-fold interpenetrated 3D frameworks with dia topology. Complexes 11 – 13 are 3D frameworks with the dmp topology and complex 14 exhibits a 2D layers with the 4L2 topology. While complex 15 exhibits a 3D framework with the neb topology, complex 18 form a 1D concave-convex chain and 19 displays a 2D structure with the 3,4,5L16 topology. The emission properties and catalytic effect on the Strecker reactions of some of the complexes are also discussed.

並列關鍵字

coordination polymer ； bis-pyridyl-bis-amide ； catalytic properties

參考文獻

(1) Hao, Y.; Wu, B.; Li, S.; Liu, B.; Jia, C.; Huang, X.; Yang, X. CrystEngComm 2011, 13, 6285-6292.

(2) Chen, B.; Eddaoudi, M.; Hyde, S. T.; O’Keeffe, M.; Yaghi, O. M. Science 2001, 291, 1021-1023.

(3) James, S. L. Chem. Soc. Rev. 2003, 32, 276-288.

(4) Bailar Jr, J. C. Prep.Inorg.React. 1964, 1, 1-27.

(5) Janiak, C. J. Chem. Soc., Dalton Trans. 2003, 2781-2804.