Title

苯咪唑四芽配子與銀、鎘離子自組裝合成與結構探討

Translated Titles

Self-Assembly and Structures of Metal-Organic Frameworks from Ag(I), Cd(II) and Flexible Benzimidazolyl Ligands

DOI

10.6841/NTUT.2006.00048

Authors

林妤芳

Key Words

超分子 ; 苯咪唑 ; 自組裝 ; 籠狀化合物 ; 配位聚合物 ; Supramolecules ; benzimidazoyl ; self-assembly ; cage ; coordination polymer

PublicationName

臺北科技大學化學工程研究所學位論文

Volume or Term/Year and Month of Publication

2006年

Academic Degree Category

碩士

Advisor

曾添文;呂光烈

Content Language

繁體中文

Chinese Abstract

本論文利用帶有四個苯咪唑配位基 (benzimidazole) 的有機配子 1,2,4,5- tetrakis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (L1) 及 1,2,4,5-tetrakis (benzimidazol-1-ylmethyl)benzene (L2),與金屬鹽類 (Ag+ 或 Cd2+) 進行室溫自組裝,得到籠狀化合物 1 , 2 及配位聚合物 3。產物結構經由單晶X射線繞射解析,並以元素分析、1H NMR、MASS、IR等儀器鑑定,再以 UV-Visible、TGA 等儀器研究化合物的性質。由單晶解析發現,化合物 1-3 皆利用苯咪唑配位基間的 π–π 微作用力,而使化合物在堆疊過程中形成更穩定的結構。 化合物 1 的化學式為 [{(L1)2Ag4(NO3)}Ag(NO3)4(CH3OH)(CH2Cl2)(H2O)]n,因配子 L1 苯環橋接的四個亞甲基碳鏈向同ㄧ方向彎曲,每一個銀離子周圍由兩個配子的咪唑N原子及一個硝酸根離子的兩個O配位,故形成四個四配位的銀離子中心,連結上下兩個苯咪唑配子而構成籠型結構,且在各籠間又存在著一個銀離子,作為橋鍵將各個籠狀化合物串聯起來,形成線性柱狀體的結構,各籠內含有兩個硝酸根陰離子。 化合物 2 的化學式為 {(L2)2Ag4(NO3)2}(NO3)2(CH3OH)2(CH2Cl2)0.5 ,與化合物1結構稍微不同,雖然也是形成籠形結構,但銀離子與兩個有機配子 (L2) 的咪唑N原子及硝酸根離子上的O原子,形成四個三配位銀離子中心,構成籠狀結構單元,這些籠型結構間,由於 L2 上無甲基的立體障礙關係,而改採錯開平行排列方式,再藉著苯咪唑上的π-π作用力進行堆疊,最後形成鋸齒狀 (zigzag) 的結構體,在各籠內含一個硝酸根陰離子。 化合物 3 的化學式為 [{Cd(L1)(CH3OH)4}(ClO4)2(CH3OH)2.5]n,其鎘離子與兩個有機配子 (L1) 上的兩個苯咪唑N原子(位在苯環的 1- 與 4- 位置),及四個甲醇分子的O原子形成六配位八面體模式,且各配子間是以 trans 的形態與鎘金屬配位,使化合物 3 的結構是以一維線性鋸齒狀呈現,而在一維線性與另一線性之間,由於上下兩對苯咪唑環基以面對面排列方式,故呈現π-π堆疊微作用力,使化合物 3 進而堆疊為三維蜂巢狀結構,在構成的網狀結構中形成多孔渠道,在各穴中包含兩個半的甲醇分子及兩個過氯酸根離子。

English Abstract

Two tetrapodal ligands with benzimidazole group, 1,2,4,5-tetrakis(5,6-dimethyl- benzimidazol-1-ylmethyl)benzene (L1) and 1,2,4,5-tetrakis(benzimidazol-1-ylmethyl)- benzene (L2), were synthesized and utilized in this study. Self-assembly of L1 and L2 with AgNO3 at room temperature gave cage-like coordination polymers {[(L1)2Ag4(NO3)2]Ag(NO3)3(CH3OH)(CH2Cl2)(H2O)4}n ( 1 ) and {(L2)2Ag4(NO3)2}- (NO3)2(CH3OH)2(CH2Cl2)0.5 ( 2 ), respectively. Reaction of L1 with Cd(ClO4)2 under mild reaction conditions afforded a porous framework [{(L2)2Ag4(NO3)2}(NO3)2 (CH3OH)2(CH2Cl2)0.5]n ( 3 ). Compounds 1-3 were characterized by element analysis, 1H-NMR, UV-Visible, Mass, IR, TGA, etc. Their structures were further determined by single-crystal X-ray diffraction analysis. For compounds ( 1 ) and ( 2 ), the benzimidazole rings are connected via intermolecular π–π stacking interation to form 3-D cage-like architecture. Compound 1 was characterized as a coordination polymer [{(L1)2Ag4(NO3)2}- Ag(NO3)3(CH3OH)(CH2Cl2)(H2O)4]n. The Ag(I) ion is coordinated by two oxygen atoms from NO3- group and two benzimidazoyl nitrogen atoms from two distinct L1 ligands. Ag(I) ion is served as a node to connect two neighboring cages, thereby constructing a rodelike structure. Compound 1 is crystallized in the triclinic system, a = 8.2427(16) Å, b = 17.470(4) Å, c = 18.923(4) Å,

Topic Category 工程學院 > 化學工程研究所
工程學 > 化學工業
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