本文選題：配位聚合物 + 咪唑　； 參考：《吉林大學(xué)》2016年碩士論文

【摘要】：近幾十年來,合理地設(shè)計(jì)合成結(jié)構(gòu)新穎、性質(zhì)優(yōu)異的配位聚合物,吸引了越來越多研究者的目光,成為熱點(diǎn)課題之一。眾所周知,構(gòu)建配位化合物主要是通過有機(jī)配體和金屬離子的配位自組裝。因此,有機(jī)配體和金屬離子的選擇,在配合物的合成中顯得尤為重要。在眾多的有機(jī)配體中,通常選擇包含羧酸、含氮雜環(huán)的有機(jī)化合物作為有機(jī)連接體。而含有咪唑基的有機(jī)化合物作為含氮雜環(huán)中的重要組成部分,一直備受研究者的關(guān)注。咪唑環(huán)中的N原子是很好的π給電子體,易和中心金屬離子配位,而且咪唑中的芳環(huán)可以產(chǎn)生π-π堆積,這樣由含咪唑基配體構(gòu)筑的配位聚合物通常都具有較好的熒光性質(zhì),常被應(yīng)用于發(fā)光材料領(lǐng)域,如:電致發(fā)光二極管、熒光探針、爆炸物的檢測(cè)。同時(shí),d10構(gòu)型的金屬Ag+、Zn2+具有眾多的配位模式,可以形成不同的網(wǎng)狀結(jié)構(gòu),并且越來越多的金屬銀(鋅)配位聚合物在室溫下展現(xiàn)了優(yōu)異的熒光性質(zhì),是潛在的光學(xué)材料。本論文根據(jù)晶體工程學(xué)原理,選取含有雙咪唑基的配體3,5-二咪唑苯腈(DICN)和3,5-二苯并咪唑基苯腈(DBIBN),水熱條件下,它們發(fā)生原位反應(yīng)生成配體DIBAH及DBIBAH,配體DIBA-、DICN及DBIBA-和金屬銀、鋅配位得到了10個(gè)具有熒光性質(zhì)的配位聚合物。Ag(DIBA)H2O(1-3),Ag(DICN)Cl O4(4),Ag(DBIBA)(5),Zn(DIBA)(BDC)0.5(6),(H2BDC=對(duì)苯二甲酸),Zn(DBIBA)NO3H2O(7),Zn(DBIBA)Cl(8),Zn(DIBA)Cl(9),Zn(DIBA)Cl(H2O)0.5(10)。化合物1-3是具有2D層狀結(jié)構(gòu)的配合物,結(jié)構(gòu)中存在著Ag…Ag鍵和π…π相互作用,分子中的振動(dòng)導(dǎo)致了1D鏈間的Ag…Ag鍵和π…π相互作用發(fā)生改變,從而影響了它們的熒光性質(zhì),使它們?cè)谑覝叵鲁尸F(xiàn)出不同顏色的熒光�；衔�4是由相互垂直的1D鏈連接成2D的層狀結(jié)構(gòu),并且在室溫下有很強(qiáng)藍(lán)綠色的熒光性質(zhì),化合物5是具有波浪型2D層狀結(jié)構(gòu)的化合物,同時(shí)室溫下展現(xiàn)出很強(qiáng)的熒光性質(zhì)�；衔�6-10是由金屬Zn與含雙咪唑基配體構(gòu)筑的化合物�；衔�6是由兩個(gè)雙層相互穿插形成的一個(gè)2D層狀配合物。它在室溫下表現(xiàn)出強(qiáng)的藍(lán)色熒光性質(zhì)�；衔�7-8屬于同種構(gòu)型晶體,均為2D層狀結(jié)構(gòu),由于結(jié)構(gòu)中配位陰離子不同,使它們的熒光性質(zhì)稍有區(qū)別�；衔�9-10均是2D層狀結(jié)構(gòu),雖然它們之間的結(jié)構(gòu)稍有不同,但是熒光性質(zhì)有很大差別,室溫下,化合物9表現(xiàn)出黃色熒光,而化合物10卻表現(xiàn)出了藍(lán)色熒光,由此可見結(jié)構(gòu)對(duì)熒光性質(zhì)的影響很大。
[Abstract]:In recent decades, the rational design and synthesis of coordination polymers with novel structure and excellent properties have attracted more and more researchers' attention and become one of the hot topics. It is well known that the construction of coordination compounds is mainly through the coordination of organic ligands and metal ions self-assembly. Therefore, the selection of organic ligands and metal ions is particularly important in the synthesis of complexes. Among many organic ligands, organic compounds containing carboxylic acids and nitrogen heterocycles are usually selected as organic connectors. As an important component of nitrogen heterocycles, imidazolyl organic compounds have attracted much attention. The N atom in imidazole ring is a good 蟺 donor, it is easy to coordinate with the central metal ions, and the aromatic ring in imidazole can produce 蟺-蟺 stacking, thus the coordination polymers constructed by imidazolyl ligands usually have better fluorescence properties. Often used in the field of luminescent materials, such as: electroluminescent diodes, fluorescent probes, explosives detection. At the same time, Ag ~ (2 +) Zn _ (2) with d _ (10) configuration has many coordination modes, which can form different network structure, and more Ag (Zn) coordination polymers exhibit excellent fluorescence properties at room temperature and are potential optical materials. According to the principle of crystal engineering, the ligands (DICN) and dibenzimidazolyl benzonitrile (DICN) and dibenzimidazolyl benzonitrile (DBIBN) containing bisimidazolyl group were selected in this paper. Under hydrothermal conditions, the ligands DIBAH and DBIBAH, the ligands DIBA-DICN and DBIBA- and metallic silver were synthesized in situ under hydrothermal conditions, and the ligands DIBA-DICN and DBIBA- and silver were obtained. Ten coordination polymers with fluorescence properties, I. e. Ag-DIBAH _ 2O _ 1-3O _ (+) Ag-DICNN, Cl _ (4) O _ (4) ~ (4) ~ (5) ~ (5) ~ (-) ~ (+) ~ (-) ~ (5) ~ (1) ~ (1) ~ (1) ~ (2) ~ (-) ~ (1) ~ (1) ~ (1) and () ~ (10) ~ (-) ~ (10) ~ (-) ~ (10) for zinc coordination polymer. Compound 1-3 is a complex with 2D layered structure, in which Ag 鈥，

本文編號(hào)：1876720