含磷酸基金屬配位聚合物之合成、結構分析與物性探討

Synthesis, Characterization and Physical Properties of Phosphonate-Containing Coordination Polymers

宋育溏(Yu-Tang Song)

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(2009年)

https://doi.org/10.6841/NTUT.2009.00134

摘要

本論文研究旨趣為將含有磷酸基的有機配位子L1、L2 (L1 = benzene-1,2,4,5-tetrayltetrakis(methylene) tetraphosphonic acid； L2 = 2,4,6-tris(phosphomethyl)mesitylene)與鹼金族(NaI, KI, CsI)，鹼土族(MgII, CaII)，過渡金屬(CuII, CoIII, NiII)，鉛(PbII)等離子，利用室溫擴散自組裝合成法與水熱自組裝合成法，製備具有有機-無機金屬混成孔洞配位聚合物。

本論文探討所合成的13種有機-無機配位聚合物（metal-organic coordinate-on polymer），分別為{[Cu2(L1)(2H2O)]•H2O}n (1)、[Co6(L2)2(4H2O)]n (2)、[Cu4(L2)2(4H2O)]n (3)、{Na4[Mg(H2O)6]2[Mg2(L2)2(H2O)18]•12H2O} (4)、{K2[Mg(H2O)6]2[Mg3(L2)2(H2O)20]•13H2O}n (5)、 {Cs4[Mg(H2O)6]4(L2)2•16H2O} (6)、{K6[Ni(H2O)6][Ni2(L2)2(H2O)25]•2H2O}n (7)、{K4[Ca4(L2)2(H2O)24]•6H2O}n (8)、{[Pb4(L2)2(H2O)4]•6H2O}n (9)、{Na5[Co(H2O)6]2(L2)2(H2O)14•0.5C2H2O4} (10)、{[Mg(H2O)6]2[Mg(L2)(H2O)5]•6H2O} (11)、{[Co(H2O)6]2[Co(L2)(H2O)5]•6H2O} (12)、{[Ni(H2O)6]2[Ni(L2)(H2O)5]•6H2O} (13)之結構與物理。

於論文中，將分為四部分探討，第一部分的主題為在水熱環境下，由有機配位子L1、L2所形成的三種晶體，分別為三維結構的{[Cu2(L1)(2H2O)]•H2O}n (1)、[Co6(L2)2(4H2O)]n (2)和二維結構的[Cu4(L2)2(4H2O)]n (3)，並探討其結構特性、熱穩定及其他物性上的鑑定分析。

第二部分針對在室溫自組裝的條件下，由有機配位子L2和鹼金族離子(NaI, KI, CsI)與鹼土族離子(MgII)所形成的三種晶體，分別為一維結構的{K2[Mg(H2O)6]2[Mg3(L2)2(H2O)20]•13H2O}n (5) 和兩個單體性結構的{Na4[Mg(H2O)6]2[Mg2(L2)2(H2O)18]•12H2O} (4)、{Cs4[Mg(H2O)6]4(L2)2•16H2O} (6)。

第三部分則針對在室溫自組裝的條件下，由有機配位子L2和鹼金族離子(NaI, KI)，鹼土族離子(CaII)，過渡金屬離子(CuII, CoIII, NiII)，鉛離子(PbII)所形成的四種晶體分別為二維結構的{K6[Ni(H2O)6][Ni2(L2)2(H2O)25]•2H2O}n (7)、{K4[Ca4(L2)2(H2O)24]•6H2O}n (8)，{[Pb4(L2)2(H2O)4]•6H2O}n (9)為一維結構，{Na5[Co(H2O)6]2(L2)2(H2O)14•0.5C2H2O4} (10)為單體分子。

第四部分乃針對藉由拆解－重組的方式，探討可水溶性之金屬－有機配位聚合物（5），使之溶於純水或含過渡金屬硝酸鹽(Co(NO3)2．6H2O 和 Ni(NO3)2．6H2O)水溶液中，進而讓5有機會重新再作組合，轉變成新的化合物（11∼13）。其結構已藉由單晶及粉末繞射技術加以鑑定，其結構上，都因鉀離子(KI)的離去而產生變化，可說是一個非常特殊的現象。

關鍵字

超分子化學 ； 配位聚合物 ； 自組裝 ； 磷酸 ； 結構

並列摘要

In this thesis, two types of ligands, benzene-1,2,4,5-tetrayltetrakis(methylene) tetraphosphonic acid (L1), 2,4,6-tris(phosphomethyl)mesitylene (L2) were reacted with alkali ions (NaI, KI, CsI), alkaline earth ions (MgII, CaII), transition-metal ions (CuII, CoII, NiII) , lead ion (PbII), respectively. Several metal–organic coordination polymers, {[Cu2(L1)(2H2O)]•H2O}n (1), [Co6(L2)2(4H2O)]n (2), [Cu4(L2)2(4H2O)]n (3), {Na4[Mg(H2O)6]2[Mg2(L2)2(H2O)18]•12H2O} (4), {K2[Mg(H2O)6]2[Mg3(L2)2(H2O)20]•13H2O}n (5) , {Cs4[Mg(H2O)6]4(L2)2•16H2O} (6), {K6[Ni(H2O)6][Ni2(L2)2
(H2O)25]•2H2O}n (7), {K4[Ca4(L2)2(H2O)24]•6H2O}n (8), {[Pb4(L2)2(H2O)4]•6H2O}n (9) , {Na5[Co(H2O)6]2(L2)2(H2O)14•0.5C2H2O4} (10), {[Mg(H2O)6]2[Mg(L2)(H2O)5]•6H2O} (11), {[Co(H2O)6]2[Co(L2)(H2O)5]•6H2O} (12), {[Ni(H2O)6]2[Ni(L2)(H2O)5]•6H2O} (13) were successfully synthesized.

The first part of this thesis reports on the hydrothermal synthesis a 3D coordination polymer {[Cu2(L1)(2H2O)]•H2O}n (1), a 2D coordination polymer [Co6(L2)2(4H2O)]n (2), and a 3D coordination polymer [Cu4(L2)2(4H2O)]n (3), thesis will discuss the structures, thermal stability and physical properties of the products.

The second part will focus on the reaction of alkali ions (NaI, KI, CsI), and alkaline earth ion (MgII) with L2 under room temperature conditions produced a 1D coordination polymer {Na4[Mg(H2O)6]2[Mg2(L2)2(H2O)18]•12H2O} (4), and two discrete structures {K2[Mg(H2O)6]2[Mg3(L2)2(H2O)20]•13H2O}n (5), {Cs4[Mg(H2O)6]
4(L2)2•16H2O} (6).

The third part will focus on the reaction of alkali ions (NaI, KI), alkaline earth ion (CaII), transition-metal ions (CoII, NiII) , and lead ion (PbII) with L2 under room temperature conditions produced a 2D coordination polymer {K6[Ni(H2O)6][Ni2(L2)2(H2O)25]•2H2O}n (7)、 {K4[Ca4(L2)2(H2O)24]•6H2O}n (8), and a 1D coordination polymer {[Pb4(L2)2(H2O)4]•6H2O}n (9), and a discrete structure {Na5[Co(H2O)6]2(L2)2(H2O)14•0.5C2H2O4} (10).

The fourth part of Ion-exchange studies, by treating 4 in water or an aqueous solution of Transition-metal nitrate (Co(NO3)2．6H2O and Ni(NO3)2．6H2O), revealed that a surprisingly dissolution/reassembly process occurred, leading to the rearrangement of metal-phosphonate building blocks and the formation of new metal-phosphonate species (11∼13). The structural transformations were confirmed by single-crystal and powder X-ray diffraction (PXRD) data.

並列關鍵字

supramolecule ； coordination polymers ； self-assembly

參考文獻

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