含N,N’-二-(3-吡啶)對苯二甲醯胺與多羧酸配位基之二價配位高分子：結構多樣性與轉換

Structural Diversity and Transformation of Divalent Coordination Polymers Constructed From N,N'-Bis(3-pyridyl)terephthalamide and Polycarboxylic Acids

陳家柔(Chia-Jou Chen)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2020年)

https://doi.org/10.6840/cycu202000254

摘要

本篇論文藉由不同的多羧酸配位基與雙醯胺雙吡啶配位基，N,N'-Bis(3-pyridyl)terephthalamide (L)與 N,N'-Bis(4-pyridyl)terephthalamide (L2)，搭配數種二價過渡金屬鹽類以水熱法成功合成出14種配位高分子：{[Cd(L)(1,3,5-HBTC)]∙2H2O}n (1,3,5-H3BTC = benzene-1,3,5-tricarboxylic acid), 1, {[Cd(L)(5-tert-IPA)(H2O)]∙2H2O}n (5-tert-H2IPA = 5-tert-butylbenzene-1,3-dicarboxylic acid), 2, [Cd(L)0.5(1,2-BDC)(H2O)]n (1,2-H2BDC = benzene-1,2-dicarboxylic acid), 3, {[Cd(L)0.5(1,4-BDC)(H2O)2]∙H2O}n (1,4-H2BDC = benzene-1,4-dicarboxylic acid), 4, {[Cd(1,3-BDC)(H2O)3]∙2H2O}n (1,3-H2BDC = benzene-1,3-dicarboxylic acid), 5, {[Cu(L)(1,3,5-HBTC)]∙H2O}n, 6, [Cu(L)0.5(5-tert-IPA)]n, 7, {[Ni(L)(1,3,5-HBTC)(H2O)]∙2H2O∙0.5L}n, 8, {[Ni(L)1.5(5-tert-IPA)(H2O)2]∙2.5H2O}n, 9, {[Ni(L)(5-tert-IPA)(CH3OH)]∙2CH3OH}n, 10, {[Zn(L)(1,3,5-HBTC)]∙2H2O}n, 11, [Zn(L)0.5(5-tert-IPA)]n, 12, {[Ni(L2)(5-tert-IPA)(H2O)]∙2H2O}n, 13, {[Ni1.5(L)1.5(1,3,5-BTC)]∙4CH3OH}n, 14, 以上化合物皆由X-光單晶繞射儀鑑定其結構，並以粉末X-光繞射儀與熱重分析儀來研究特性。
　　化合物1, 3, 6, 11與13為具有sql拓譜學的二維層狀結構，化合物2和9為一維的梯子結構，化合物4為具有hcb拓譜學的二維層狀結構，化合物7與12為具有cds拓譜學的三維網狀結構並具有3-fold相互貫穿，化合物8為具有2,4C6拓譜學的一維通道結構，化合物10為具有2,4L2拓譜學的二維層狀結構，化合物14為具有3,4,4L35拓譜學的二維層狀結構，而化合物5則是一維鋸齒結構。有趣的是，化合物9與10以及化合物8與14之間在溶劑的置換具有獨特的結構轉換，而化合物1 - 5，11與12具有發光特性。

關鍵字

配位高分子 ； 雙醯胺雙?啶 ； 結構轉換 ； 拓譜學

並列摘要

The syntheses, structures and properties of a series of coordination polymers constructed from polycarboxylic acids, N,N'-bis(3-pyridyl)terephthalamide (L), N,N'-bis(4-pyridyl)terephthalamide (L2) and transition metal salts are reported, including {[Cd(L)(1,3,5-HBTC)]∙2H2O}n (1,3,5-H3BTC = benzene-1,3,5-tricarboxylic acid), 1, {[Cd(L)(5-tert-IPA)(H2O)]∙2H2O}n (5-tert-H2IPA = 5-tert-butylbenzene-1,3-dicarboxylic acid), 2, [Cd(L)0.5(1,2-BDC)(H2O)]n (1,2-H2BDC = benzene-1,2-dicarboxylic acid), 3, {[Cd(L)0.5(1,4-BDC)(H2O)2]∙H2O}n (1,4-H2BDC = benzene-1,4-dicarboxylic acid), 4, {[Cd(1,3-BDC)(H2O)3]∙2H2O}n (1,3-H2BDC = benzene-1,3-dicarboxylic acid), 5, {[Cu(L)(1,3,5-HBTC)]∙H2O}n, 6, [Cu(L)0.5(5-tert-IPA)]n, 7, {[Ni(L)(1,3,5-HBTC)(H2O)]∙2H2O∙0.5L}n, 8, {[Ni(L)1.5(5-tert-IPA)(H2O)2]∙2.5H2O}n, 9, {[Ni(L)(5-tert-IPA)(CH3OH)]∙2CH3OH}n, 10, {[Zn(L)(1,3,5-HBTC)]∙2H2O}n, 11, [Zn(L)0.5(5-tert-IPA)]n, 12, {[Ni(L2)(5-tert-IPA)(H2O)]∙2H2O}n, 13, {[Ni1.5(L)1.5(1,3,5-BTC)]∙4CH3OH}n, 14. Their structures hane been determined by single-cryatal X-ray diffraction analyses and characterized by powder X-ray diffraction and thermal gravimetric analysis.
Complexes 1, 3, 6, 11 and 13 are 2D layers with the sql topology, complexes 2 and 9 are 1D ladders, complex 4 is a 2D layer with the hcb topology, complexes 7 and 12 are 3-fold interpenetrated 3D nets with the cds topology, complex 8 shows a 1D channel with the 2,4C6 topology, complex 10 is a 2D layer with the 2,4L2 topology, complex 14 is a 2D layer with the 3,4,4L35 topology and complex 5 forms a 1D zigzag chain. Moreover, complexes 9 and 10 display irreversible structural transformation upon solvent exchange, as well as complexes 8 and 14. The luminescencnt properties of complexes 1 - 5, 11 and 12 are also discussed.

並列關鍵字

Coordination Polymer ； Bis-pyridyl-bis-amide ； Structural Transformation ； Topology

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