本文選題：配位聚合物 + 鑭系金屬有機框架�。� 參考：《西北大學》2017年碩士論文

【摘要】：金屬-有機框架化合物(Metal-organic Frameworks,MOFs)作為配位聚合物(Coordination Polymers,CPs)中最具研究潛力的重要一員,自上世紀90年代以來,經(jīng)歷了飛速的發(fā)展。在這個過程中,研究者們對其紛繁復雜的結構做了系統(tǒng)、深刻的研究總結,并逐漸將研究重心過渡至挖掘它們的潛在應用價值上。具有氣體吸附分離、分子識別、催化、磁性等優(yōu)良性能的功能性MOFs被廣泛構筑、研究。MOFs自組裝合成是一個復雜的反應過程,在眾多影響因素中,有機配體由于其分子尺寸不同、具有不同的官能團和配位點及對稱性的差異等,在決定目標產(chǎn)物的結構和性能時扮演了非常重要的角色。尤其是具有靈活配位模式的剛性多羧酸配體和官能化修飾的具有多配位點的N-雜環(huán)羧酸類配體往往能構筑結構多變,性能優(yōu)異,骨架穩(wěn)定的MOFs。此外,在改良功能性配合物性能時,中心金屬離子的電子結構對其性能起到了決定性的作用,鑭系金屬離子因為其獨特的4f軌道而在磁性和熒光等方面具有的特殊性能而被化學家們廣泛用于開發(fā)高性能的MOFs材料。遵循以上的構筑策略,本論文選用了帶硝基的聯(lián)苯-3'-硝基-3,4',5-三羧酸(H3L1)配體和兩個同分異構的吡啶羧酸配體2-(3,5-間苯二甲酸)-5-吡啶甲酸(H3L2)和3-(3,5-間苯二甲酸)-6-吡啶甲酸(H3L3)配體為構筑基元用來設計合成功能性配合物。在晶體工程分子自組裝原理的指引下,采用水熱溶劑熱法成功合成了以下配合物:[LnL1(H2O)3].3H2O·0.75DMF(1-7)(Ln=Dy(1),Eu(2),Tb(3),Gd(4),Er(5),Ho(6),和 Yb(7));[Ln2(L2)2(H2O)4(DMA)].DMA·3H20(Ln= Dy(8),Eu(9),Ho(10),Tb(11),Gd(12),Yb(13)和Er(14);[Zn4(L1)2(H2O)(OH)2](15);[Zn3(L3)2(H2O)]·4H20(16);[Zn3(L3)2(bipy)(H2O)6]2H20(17)。配合物1-7和8-14分別為兩個系列典型的Ln-MOFs,各自具有相同的結構,并具有優(yōu)良的磁學和光學性質。單晶X射線研究表明,配合物15是一例具有罕見的7核金屬簇的結構,相鄰的兩個金屬簇利用配體連接,構筑起三維的空間結構。配合物16和17是利用d1()電子組態(tài)金屬與H3L3設計合成的,因此都具有一定的熒光性能。本論文對合成的配合物進行了 X-射線粉末衍射(PXRD)、元素分析、紅外光譜(IR)和熱重分析(TGA)等基本表征。此外,對以上提及性質做了系統(tǒng)的探究。
[Abstract]:Metal-organic frameworks (MOFs), as one of the most promising coordination polymers, have experienced rapid development since the 1990s.In this process, the researchers made a systematic and profound summary of their complicated structures, and gradually transferred the research focus to excavating their potential application value.Functional MOFs with excellent properties such as gas adsorption and separation, molecular recognition, catalysis and magnetism have been widely constructed. Self-assembly synthesis of MOFs is a complex reaction process. Among many factors, organic ligands have different molecular sizes.Different functional groups, coordination points and symmetry play a very important role in determining the structure and properties of the target products.In particular, rigid polycarboxylic acid ligands with flexible coordination modes and N-heterocyclic carboxylic acid ligands with functionalized functionalization are often able to construct MOFs with variable structure, excellent performance and stable skeleton.In addition, the electronic structure of the central metal ions plays a decisive role in improving the properties of the functional complexes.Lanthanide metal ions have been widely used by chemists to develop high performance MOFs materials due to their special magnetic and fluorescent properties due to their unique 4f orbitals.Follow the above construction strategy,In this thesis, the ligand of biphenyls with nitro biphenyls, biphenyls, nitro, tricarboxylic acid, trichlorocarboxylic acid, and two isomerized pyridine carboxylic acid ligands, 2-Py, 5-pyridine-5-pyridinic acid, H3L2) and 3-triphenylalanedioic acid-6-pyridinoic acid (H3L3), were used as constructors for the construction of the ligands in this thesis.Design and synthesis of functional complexes.鍦ㄦ櫠浣撳伐紼嬪垎瀛愯嚜緇勮�呭師鐞嗙殑鎸囧紩涓�,閲囩敤姘寸儹婧跺墏鐑�娉曟垚鍔熷悎鎴愪簡浠ヤ笅閰嶅悎鐗�:[LnL1(H2O)3].3H2O路0.75DMF(1-7)(Ln=Dy(1),Eu(2),Tb(3),Gd(4),Er(5),Ho(6),鍜，

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