含柔性雙醯胺吡啶與多羧酸配位基之二價鎘、鈷、鎳配位高分子的合成、結構與特性研究: 結構糾纏與轉換

Syntheses, Structures and Properties of Cd(II), Co(II) and Ni(II) Coordination Polymers Containing Flexible Bis-pyridyl-bis-amide and Polycarboxylate Ligands: Structural Entanglement and Transformation

許智勛(Chih-Hsun Hsu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2017年)

https://doi.org/10.6840/cycu201700371

摘要

一系列含N,N¢-二-(3-吡啶)辛二醯二胺 (L1) ， N,N¢-二-(4-吡啶)辛二醯二胺 (L2) ， N,N¢-二-(3-吡啶)二酰己二胺 (L3) 與多羧酸配位基之二價金屬配位高分子已藉由水熱法合成。分別為:{[Cd(L1)(2,6-PDC)]·5H2O}n (2,6-H2PDC = 2,6-pyridinedicarboxylic acid), 1, {[Cd(L2)(2,6-PDC)]·2.5H2O}n, 2, {[Cd(L1)1.5(1,2,3-HBTC]·2H2O}n (1,2,3-H3BTC = 1,2,3-benzenetricarboxylic acid), 3, [Ni(L2)(1,3-PDA)(H2O)2]n (1,3-H2PDA = 1,3-phenylenediacetic acid), 4, [Co(L2)(1,3-PDA)(H2O)2]n, 5, [Co(L1)(5-NH2-IPA)]n (5-NH2-H2IPA = 5-aminoisophthalic acid), 6, {[Co(L2)0.5(5-NH-IPA)(H2O)2]．2H2O}n, 7, [Co(L1)(5-NO2-IPA)(H2O)]n (5-NO2-H2IPA = 5-aminoisophthalic acid), 8, [Co(L1)1.5(1,4-NDC)(H2O)]n (1,4-H2NDC = 1,4-naphthalenedicarboxylic acid), 9, [Co3(L1)1.5(1,4-NDC)3(EtOH)]n, 10, {[Co(L2)1.5(1,4-NDC)]．H2O}n, 11, {[Co(L2)0.5(1,4-NDC)]·(EtOH)}n, 12, {[Ni(L2)1.5(1,4-NDC)]．H2O}n, 13,與[Co(L3)(1,3,5-HBTC)(H2O)]n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid), 14。這些化合物的結構已藉由單晶X-ray繞射儀鑑定，其特性以粉末X-ray繞射儀與熱重分析儀探討。
化合物1、4、5、6、8與9具sql拓譜學的二維結構。化合物2與14具一維的環鏈狀結構。化合物3具新型(65,8)拓樸學之三維結構與(1 + 4)自我貫穿。化合物7具新型(63)(65.8)拓樸學之二維的網狀結構。化合物10具新型(48.66.8)拓樸學之三維結構與(1 + 2)自我貫穿。化合物11與13具bnn拓樸學之三維結構與5-fold相互貫穿。化合物12具pcu拓樸學之三維結構與2-fold相互貫穿。化合物4與9對於水分子具有結構再現性，而化合物9與10之間在溶劑置換具有獨特的結構轉換。化合物4與5具有增加光降解速率的特性。

關鍵字

配位高分子 ； 結構糾纏 ； 轉換

並列摘要

A series of divalent coordination polymers constructed from N,N’-di(3-pyridyl)suberoamide (L1), N,N’-di(4-pyridyl)suberoamide (L2), N,N’-di(3-pyridyl)adipamide (L3) and angular polycarboxylaic ligands, including {[Cd(L1)(2,6-PDC)]·5H2O}n (2,6-H2PDC = 2,6-pyridinedicarboxylic acid), 1, {[Cd(L2)(2,6-PDC)]·2.5H2O}n, 2, {[Cd(L1)1.5(1,2,3-HBTC]·2H2O}n (1,2,3-H3BTC = 1,2,3-benzenetricarboxylic acid), 3, [Ni(L2)(1,3-PDA)(H2O)2]n (1,3-PDA = 1,3-phenylenediacetic acid), 4, [Co(L2)(1,3-PDA)(H2O)2]n, 5, [Co(L1)(5-NH2-IPA)]n (5-NH2-H2IPA = 5-aminoisophthalic acid), 6, {[Co(L2)0.5(5-NH-IPA)(H2O)2]．2H2O}n, 7, [Co(L1)(5-NO2-IPA)(H2O)]n (5-NO2-H2IPA = 5-aminoisophthalic acid), 8, [Co(L1)1.5(1,4-NDC)(H2O)]n (1,4-H2NDC = 1,4-naphthalenedicarboxylic acid), 9, [Co3(L1)1.5(1,4-NDC)3(EtOH)]n, 10, {[Co(L2)1.5(1,4-NDC)]．H2O }n, 11, {[Co(L2)0.5(1,4-NDC)]·(EtOH)}n, 12, {[Ni(L2)1.5(1,4-NDC)]．H2O }n, 13, and [Co(L3)( 1,3,5-HBTC) (H2O)]n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid), 14, have been synthesized by 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, 4, 5, 6, 8 and 9 are 2D layers with the sql topology and 2 and 14 form 1D looped chains, while 3 exhibits a 3D framework with a new (65.8) topology that shows a (1 + 4) self-penetration, and 7 displays a 2D network with a new (63)(65.8) topology. Complex 10 exhibits a 3D framework with a new (48.66.8) topology that shows a (1 + 2) self-penetration, and 11 and 13 display 5-fold interpenetrated 3D frameworks with the bnn topology, while 12 displays a 2-fold interpenetrated 3D framework with the pcu topology. While complexes 4 and 9 show structural reproducibility toward water, complexes 9 and 10 display irreversible structural transformation upon solvent exchange. Moreover, complexes 4 and 5 show catalytic effect on the photodegradation.

並列關鍵字

coordination polymer ； structure entanglement ； transformation

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