【摘要】：配位聚合物在構(gòu)筑過程中因受有機配體、中心金屬離子和反應(yīng)條件(如溫度、pH、溶劑等)等因素的影響,預(yù)測其拓撲結(jié)構(gòu)具有難度。研究這些因素影響的規(guī)律對配位聚合物的設(shè)計與合成具有指導(dǎo)意義。柔性多羧酸配體根據(jù)不同反應(yīng)條件可呈現(xiàn)不同的構(gòu)象從而構(gòu)筑出結(jié)構(gòu)豐富多樣的配位聚合物,因而吸引著眾多研究人員的興趣。本論文基于四種柔性芳香多羧酸配體與過渡金屬在水熱條件下自組裝制備得到8個配位聚合物,主要研究內(nèi)容如下:一、設(shè)計合成了四種含醚鍵(C-O-C)柔性多羧酸配體和一種含氮雜環(huán)輔配體:4,4'-(1,4-苯二氧基)雙苯甲酸(H2L1)、4,4'-(1,3-苯二氧基)雙苯甲酸(H2L2)、1,3-二[3,5-(二羧基)苯氧基]-2-羥基丙烷(H_4L_3)、均三甲苯基-1,3,5-三亞甲基氧代-間三苯二甲酸(H6L4)和1,1′-(1,4-丁基)二苯并咪唑(bbbm)。配體H2L1與H2L2含Ar-O-Ar單元,屬于既含剛性又具有柔性的半柔性多羧酸配體。配體H_4L_3與H6L4均為基于間苯二酸為構(gòu)筑單元的多羧酸柔性配體。五種配體均經(jīng)紅外(IR)、核磁共振氫譜(1H-NMR)驗證。二、基于以上柔性多羧酸配體,通過改變中心金屬離子、溶劑、pH值等條件合成了8個新穎的配位聚合物:[Mn(L1)(H_2O)2]n(1)、[Cd(L1)(H_2O)2]n(2)、[Zn(L2)(bbbm)0.5]n(3)(bbbm=1,1′-(1,4-butanediyl)bisbenzimidazole)、[Co(L2)(bbbm)]n(4)、[Cd(L2)(bbbm)]n(5)、[Cu2(L3)(H_2O)3]n(6)、[Cd2(L3)(H_2O)6]n(7)及[Cd2(L4)(H_2O)4]n(8)。通過元素分析、紅外光譜(IR)及X-射線粉末衍射(PXRD)分別對所有配合物進行表征;利用單晶X-射線衍射對配合物晶體結(jié)構(gòu)進行分析。同時,還研究了所有配合物的熱穩(wěn)定性、固體熒光性質(zhì)和部分配合物的磁學(xué)性質(zhì)。三、配合物1和2屬于同構(gòu)類型,呈現(xiàn)三維dia網(wǎng)絡(luò)拓撲結(jié)構(gòu),頂點符號為[6(2).6(2).6(2).6(2).6(2).6(2)]。配合物3、4和5是由配體H2L2構(gòu)筑的二維配位聚合物,其中配合物4與5為同構(gòu)類型,他們呈現(xiàn)聚輪烷和聚索烴共存的二重穿插2D網(wǎng)絡(luò)結(jié)構(gòu),Schl?fli拓撲符號為{63}。而配合物3在結(jié)構(gòu)上與配合物4和5存在較大差異,其拓撲類型為sql,點符號為(44.62)。配合物3與4/5結(jié)構(gòu)上的差異表明金屬中心離子對配位聚合物的框架結(jié)構(gòu)存在明顯的影響。配合物4和5在熒光和磁性方面存在較大的差異,這也表明金屬中心離子對配位聚合物的性能存在顯著的影響。四、配合物6是基于H_4L_3構(gòu)筑的三維拓撲類型,Schl?fli符號為{42.64}{42.84}。該配合物通過有機配體陰離子將kagomé型二維網(wǎng)絡(luò)聯(lián)接成三維網(wǎng)絡(luò)結(jié)構(gòu),結(jié)構(gòu)中含有兩種大小的孔徑,具有潛在的吸附性能。磁學(xué)研究表明,該配合物內(nèi)部主要呈現(xiàn)反鐵磁相互作用。配合物7和8是分別基于配體H_4L_3和H6L4的二維配位聚合物,它們具有相同的點符號(63)。配合物7呈現(xiàn)ABCABC堆積,而配合物8則以ABAB形式堆積。兩者都有較好的熱穩(wěn)定性及熒光性能,可用作功能性發(fā)光材料。
[Abstract]:It is difficult to predict the topological structure of coordination polymers due to the influence of organic ligands, central metal ions and reaction conditions (such as temperature, pH, solvent, etc.). The study of the influence of these factors on the design and synthesis of coordination polymers is of great significance. Flexible polycarboxylic acid ligands can present different conformation according to different reaction conditions, and thus construct coordination polymers with rich and diverse structures, which has attracted the interest of many researchers. In this thesis, eight coordination polymers were prepared by self-assembly of four flexible aromatic polycarboxylic acid ligands and transition metals under hydrothermal conditions. The main contents are as follows: 1. Four kinds of flexible polycarboxylic acid ligands containing ether bond (C-O-C) and a nitrogen-containing heterocyclic coligand, 1: 4- (1o 4- phenyldioxy) dibenzoic acid (H2L1) 4- (1, 3-phenyldioxy) dichlorobenzoic acid (H2L2), 13-bis (dicarboxylic) phenoxy] -2-hydroxypropane (H_4L_3), are designed and synthesized. Trimethylenedioxylic acid (H6L4) and 1-dibenzimidazole (bbbm). Ligands H2L1 and H2L2 contain Ar-O-Ar units and belong to semi-flexible polycarboxylic acid ligands with rigidity and flexibility. Both ligands H_4L_3 and H6L4 are polycarboxylic acid flexible ligands based on isophthalic acid. The five ligands were confirmed by (IR), NMR hydrogen NMR (1H-NMR). 浜，

本文編號：2226986