本文選題：配位聚合物 + 多羧酸配體��； 參考：《中北大學(xué)》2017年碩士論文

【摘要】：近些年來,由于配位聚合物的結(jié)構(gòu)的多樣性和潛在的應(yīng)用價值引起了化學(xué)和材料學(xué)科等領(lǐng)域的科學(xué)家們的廣泛的關(guān)注。設(shè)計合成由含氧羧酸、含氮雜環(huán)以及含氮含氧混合配體構(gòu)筑的結(jié)構(gòu)新穎、性能優(yōu)異的配位聚合物,已成為配位化學(xué)的一個研究的熱點。由于配位聚合物自組裝過程受到多因素的影響,例如溫度、反應(yīng)時間、p H值、溶劑、配體、金屬離子、配體和金屬離子的比例等,其中最重要的影響因素為配體和金屬離子的合理選擇。基于此本文選擇偶氮苯-3,3',5,5'-四羧酸(H_4abtc)配體和1,3-[(8-羥基-5喹啉)偶氮]-苯二甲酸(H_3qapc)作為有機橋連體,利用水熱和溶劑熱合成法,成功合成了八個新型的稀土金屬配合物。并且進(jìn)行了晶體結(jié)構(gòu)分析、元素分析、紅外分析、紫外分析,熱穩(wěn)定性分析,并對部分配合物的磁性和熒光性質(zhì)進(jìn)行了研究。為了進(jìn)一步拓展本課題組之前合成的配合物的應(yīng)用價值,并對之前采用1-(苯并三氮唑-1-甲基)-1-(2-丙基咪唑)含氮配體(bpmi)成功合成的4個二價銅配位聚合物[Cu(bpmi)2(Ac)2]·H_2O(9),[Cu(bpmi)2(H_2O)2]·2NO3·2H_2O(10),[Cu(bpmi)(N3)2](11)以及[Cu3(bpmi)2(SCN)4(DMF)](12)進(jìn)行了磁性的研究。主要內(nèi)容如下:1.以偶氮苯-3,3',5,5'-四羧酸為配體,合成了5個稀土金屬配位聚合[Dy(Habtc)(H_2O)_3]·2H_2O(1)、[Eu(H_3abtc)2(DMF)_3(H_2O)]·2H_2O(2)、[Nd3(abtc)2.5(H_2O)6.5](3)、[La3(abtc)2.5(H_2O)6.5](4)和[Y(abtc)(H_2O)](5)單晶X-射線衍射分析表明配合物1和配合物5均為具有兩種1D孔道的三維網(wǎng)絡(luò)結(jié)構(gòu),配合物2為一維鏈狀結(jié)構(gòu),配合物3和4同構(gòu),為具有1D孔道的二維結(jié)構(gòu)。其中,在配合物的自組裝過程中,可以看到多羧酸類配體反應(yīng)體系的去質(zhì)子化程度對配合物結(jié)構(gòu)的多樣性有重要的影響。在配合物2-4的結(jié)構(gòu)中存在微弱的p-p共軛、氫鍵相互作用。2.以1,3-[(8-羥基-5喹啉)偶氮]-苯二甲酸為配體,合成了3個稀土金屬配位聚合物Dy(qapc)(H_2O)2]·2H_2O(6)、[Y(qapc)(H_2O)2]·2H_2O(7)和[Nd2(H_2qapc)2(Hqapc)2(H_2O)10]·6H_2O(8)。單晶X-射線衍射分析表明配合物6和配合物7為同構(gòu),均為具有1D孔道的三維網(wǎng)絡(luò)結(jié)構(gòu)。配合物8為雙核零維結(jié)構(gòu)。在配合物8的結(jié)構(gòu)中存在微弱的氫鍵相互作用。3.室溫下對自由配體H_4abtc和H_3qapc以及配合物1,3-8的固態(tài)熒光性能進(jìn)行測試,結(jié)果表明不同的稀土金屬對配體H_4abtc和H_3qapc的熒光性質(zhì)具有不同程度的影響。4.在溫度范圍為2-300 K和1000 Oe的外磁場條件下測定配合物6變溫磁化率,結(jié)果表明配合物6的磁性中心具有反鐵磁耦合作用。5.對配合物1-8的熱穩(wěn)定性進(jìn)行了研究。6.在溫度范圍為2-300 K和1000 Oe的外磁場條件下測定配合物9-12變溫磁化率,結(jié)果表明配合物9-12的磁性中心均具有反鐵磁耦合作用。
[Abstract]:In recent years, due to the diversity of coordination polymer structures and potential applications, scientists in the field of chemistry and materials have attracted wide attention. The design and synthesis of novel coordination polymers composed of oxygen-containing carboxylic acids, nitrogen-containing heterocycles and nitrogen-containing oxygen-containing ligands have become a hotspot in coordination chemistry. The self-assembly process of coordination polymers is affected by many factors, such as temperature, reaction time, pH value, solvent, ligand, metal ion, ratio of ligand to metal ion, etc. The most important factor is the rational selection of ligand and metal ions. Based on this, eight new rare earth metal complexes have been successfully synthesized by hydrothermal and solvothermal synthesis. The crystal structure analysis, elemental analysis, infrared analysis, UV analysis, thermal stability analysis were carried out. The magnetic and fluorescence properties of some complexes were also studied. In order to further expand the application value of the complexes synthesized before our research group, The magnetic properties of four divalent copper-coordination polymers [Cu(bpmi)2(Ac)2] H _ 2O _ 9, [Cu(bpmi)2(H_2O)2] 2NO3 _ 2H _ 2O _ (10), [Cu(bpmi)(N3)2] _ (11) and [Cu _ 3bpmio _ 2SCN _ 4 (DMF)], which were successfully synthesized by 1-( benztriazole-1-methyl-2-propyl imidazole) N-containing ligands, [Cu(bpmi)2(Ac)2] H _ 2O-9N, [Cu(bpmi)2(H_2O)2] 2NO3 _ 2H _ 2O-10, [Cu(bpmi)(N3)2] _ (11) were studied. The main content is as follows: 1. 浠ュ伓姘嫰-3,3',5,5'-鍥涚晶閰鎬負(fù)閰嶄綋,鍚堟垚浜，

本文編號：1908901