稀土金属有机框架的合成、结构及其性能研究

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英文题名：Synthesis, Structure, and Performance of the Lanthanide Meatal-Organic Frameworks 作者：唐群 论文级别：博士 学科专业名称：无机化学 中文关键词：稀土 ; 金属-有机框架 ; 合成 ; 发光 ; 质子传导 英文关键词：Lanthanide ; Metal-Organic Framework ; Synthesize ; Luminescence ; Proton 英文关键词：Conduction 学位年度：2014 导师：刘术侠 学科代码：070301 学位授予单位：东北师范大学 论文提交日期：2014-06-01

摘要

由于在光、电、磁、催化领域尤其是发光方面的优异性能，稀土金属有机框架(Ln-MOFs)化合物受到人们越来越多的关注。稀土离子具有独特的4f电子组态，与有机配体结合后，由于协同效应的影响可以得到许多结构多样、性能优异的Ln-MOFs化合物。本论文通过常规和溶剂热等合成方法，利用有机配体桥联稀土离子，组装成系列Ln-MOFs化合物，表征它们的单晶结构、发光性质、磁性以及质子传导等性能。主要创新性工作分为以下几个方面：
     1.选用有机配体H3BTPCA (2,4,6-三异哌啶酸-1,3,5-三嗪)，在温和的溶剂热合成条件下，组装得到系列新颖的微孔Ln-MOFs化合物：[Ln(BTPCA)(H2O)]·2DMF·3H2O（Ln=Eu3+(1)，Ce3+(2)，Pr3+(3)，Nd3+(4); DMF=N,N-二甲基甲酰胺）。这些Ln-MOFs通过稀土离子的一维链连接有机配体构成三维框架结构，沿c轴方向具有两种孔道，同时具有较高的热稳定性和结构稳定性。Eu3+-MOFs的发光性质被详细的研究，在配体的敏化作用下，其发光被有效增强。这些Ln-MOFs具有多个路易斯碱活性位点，并指向孔道的内部，能够与客体金属离子相互作用，考虑用作金属离子的传感。这里我们深入研究了Eu-MOFs的发光性质及其对金属离子传感的作用机理。[Eu(BTPCA)(H2O)]·2DMF·3H2O (1)[Ce(BTPCA)(H2O)]·2DMF·3H2O (2)[Pr(BTPCA)(H2O)]·2DMF·3H2O (3)[Nd(BTPCA)(H2O)]·2DMF·3H2O (4)
     2.进一步合成了系列同构的Ln-MOFs：[Ln(BTPCA)(H2O)]·2DMF·3H2O （Ln=La3+(5)，Sm3+(6)，Tb3+(7)）。这一系列Ln-MOFs中，不同的稀土离子的配位环境都相同，可以通过原位掺杂的方法来实现不同稀土离子存在同一框架结构中，从而制备出混合金属中心的Ln-MOFs同似物。根据三原色原理，通过调节掺入初始反应物的稀土离子浓度来调控Ln-MOFs同似物不同的光发射颜色，以及获得最优化的白光发射材料。对于这类Ln-MOFs的发光性质可能的响应机理也被研究。[La(BTPCA)(H2O)]·2DMF·3H2O (5)[Sm(BTPCA)(H2O)]·2DMF·3H2O (6)[Tb(BTPCA)(H2O)]·2DMF·3H2O (7)
     3.利用稀土Gd3+与有机配体H3BTPCA构筑一个同构的Gd-MOF（化合物8），BTPCA配体的羧酸基团桥接钆离子形成一维的稀土链结构，Gd3+···Gd3+之间距离较小（4.046(3)）且Gd3+Gd3+Gd3+键角较大（171.375(18)°）。对该化合物8的磁性质进行详细的研究，表明这个化合物具有弱的铁磁性相互作用；同时在温度为3K以及磁场为7T时，化合物8的磁熵变达到最大值为20.40J kg–1K–1；较高的磁热效应暗示了其在超低温磁制冷方面潜在的应用前景。[Gd(BTPCA)(H2O)]·2DMF·3H2O (8)
     4.利用稀土碳酸盐和草酸反应，在溶剂热合成条件下，组装得到一个新颖的微孔的Ln-MOF化合物：[Eu2(CO3)(ox)2(H2O)2]·4H2O (9, ox=草酸)，首次得到了在温度高于100oC和无外加湿度条件下水体系的高质子传导。这个Ln-MOF是由一维的稀土碳酸带连接草酸配体构成三维框架结构，沿a轴方向具有有序的一维孔道，同时稀土离子上的配位水分子指向孔道的内部，并与邻近的草酸上的氧原子形成紧密的一维氢键通路，具有较高的热稳定性和结构稳定性。尽管化合物9是电中性的，但稀土离子上的配位水分子与邻近草酸基团上的氧相互作用有助于贡献出质子，因此增强质子传导率。此外，选择一个已报道的具有与化合物9相似活性的Ln-MOF：{[Eu(H2O)3]2(ox)3}·4H2O (10)作为参比物，来说明配位水分子与邻近的草酸上的氧原子形成的一维氢键通路的保持是质子传导的先决条件。化合物9的变温荧光性质的研究表明了配位水分对高质子传导率的贡献。[Eu2(CO3)(ox)2(H2O)2]·4H2O (9){[Eu(H2O)3]2(ox)3}·4H2O (10)
     5.在常规反应条件下，成功合成了一系列三维的多酸基稀土有机杂化化合物：[Ln2(DNBA)4(DMF)8][W6O19](Ln=La(11), Ce(12), Sm(13), Eu(14), Gd(15); DNBA=3,5-二硝基苯甲酸)。这些杂化化合物是由Lindqvist型[W6O19]2–作为阴离子，两个稀土离子桥连四个3,5-二硝基苯甲酸作为二聚阳离子[Ln2(DNBA)4(DMF)8]2+构成的。化合物14的荧光性质被详细地表征，它在溶液中的发光强度随溶剂的介电常数的增加而升高，表现了溶剂效应。其溶剂效应的作用原理通过高分辨电喷雾质谱（ESI–MS）在溶液中探究，指明了结构和发光性质的相关性。[La2(DNBA)4(DMF)8][W6O19](11)[Ce2(DNBA)4(DMF)8][W6O19](12)[Sm2(DNBA)4(DMF)8][W6O19](13)[Eu2(DNBA)4(DMF)8][W6O19](14)[Gd2(DNBA)4(DMF)8][W6O19](15)
The lanthanide metal–organic frameworks (Ln-MOFs) are attracting much attention, owing totheir excellent performance in luminescence, electricity, magnetism, and catalysis especiallyin luminescence. Lanthanide ions are characterized by a gradual filling of the4f orbitals.The combination of organic ligands and lanthanide ions can obtain diverse geometric patternsand remarkable physical and chemical properties by synergistic effect. In this paper, a seriesof crystalline Ln-MOFs materials are synthesized by the advisable organic ligands andlanthanide ions, and the structure and performance of Ln-MOFs are characterized. The maininnovative work as follows:
     1. Under conventional reaction conditions, a series of novel Ln-MOFs[Ln(BTPCA)(H2O)]·2DMF·3H2O (Ln=Eu3+(1), Ce3+(2), Pr3+(3), Nd3+(4); DMF=N,N-dimethylformamide) are synthesized using a ligand H3BTPCA(1,1′,1′′-(benzene-1,3,5-triyl)tripiperidine-4-carboxylic acid). The readily accessiblemultiple Lewis basic triazinyl N atoms allow for complexation of incoming metal ions guests,and such interactions are established quantitatively and unambiguously. Depending on theinteraction and the resulting perturbation to the electronic structure of the ligand, theefficiency of ligand–to–lanthanide energy transfer is affected, leading to the quenching orenhancement of luminescence. The essentially complete quenching and drastic enhancementof the Eu3+luminescence upon respective incorporation of metal ions into the inherentlyluminescent MOF suggest specifically the potential use of the MOF for metal ions sensing.[Eu(BTPCA)(H2O)]·2DMF·3H2O (1)[Ce(BTPCA)(H2O)]·2DMF·3H2O (2)[Pr(BTPCA)(H2O)]·2DMF·3H2O (3)[Nd(BTPCA)(H2O)]·2DMF·3H2O (4)
     2. The isostructural Ln-MOFs are synthesized through the spontaneous self-assembly ofH3BTPCA ligands and lanthanide ions (Ln=La3+, Tb3+, Sm3+, etc.). Prompted by theobservation that the different lanthanide ions have identical coordination environment in theseLn-MOFs, we explored and succeeded in the preparation of mixed-lanthanide analogs of thesingle-lanthanide MOFs by way of in situ doping using a mixture of lanthanide salts. Withcareful adjustment of the relative concentration of the lanthanide ions, the color of theluminescence can be modulated, and white light-emission can indeed be achieved. Themechanisms possibly responsible for the observed photophysical properties of thesemixed-lanthanide MOFs are also discussed.[La(BTPCA)(H2O)]·2DMF·3H2O (5)[Sm(BTPCA)(H2O)]·2DMF·3H2O (6) [Tb(BTPCA)(H2O)]·2DMF·3H2O (7)
     3. The isostructural Gd-MOF (8) is synthesized through H3BTPCA ligands and Gd3+ions.The adjacent Gd3+ions are bridged by carboxylic group of BTPCA ligands to generate a1Dchain structure. The adjacent Gd3+···Gd3+distance is4.046(3), and the Gd3+Gd3+Gd3+angle is171.375(18)°. The magnetic measurements show that8reveales weakferromagnetic interactions, and acts as a cryogenic magnetic refrigerant having magneticentropy change, ΔSm, of20.40J kg1K1(ΔH=7T at3K).[Gd(BTPCA)(H2O)]·2DMF·3H2O (8)4. An oxalate-and carbonate-based three dimension Ln-MOF[Eu2(CO3)(ox)2(H2O)2]·4H2O (9, ox=oxalate) is synthesized, and demonstrated the firstwater-mediated proton conduction under above100oC without humidity. Although9isneutral, coordinated water molecules are rendered sufficiently acidic by EuIIIto contributeprotons to the adjacent ox groups and thereby enhance the conductivity. The reportedcompound {[Eu(H2O)3]2(ox)3}·4H2O (10) with similar thermostability as9, is used as acomparative study to explain that1D hydrogen-bonding channel of coordinated watermolecules and the adjacent ox groups is critical importance for proton conduction. Thetemperature-dependent photoluminescent (PL) properties of9are pressed to illustrate thecontribution of the coordinated water molecules for proton conduction.[Eu2(CO3)(ox)2(H2O)2]·4H2O (9){[Eu(H2O)3]2(ox)3}·4H2O (10)
     4. Under conventional reaction conditions, a series of lanthanide-organic complexesbased on polyoxometalates (POMs)[Ln2(DNBA)4(DMF)8][W6O19](Ln=La(11), Ce(12),Sm(13), Eu(14), Gd(15); DNBA=3,5-dinitrobenzoate) are synthesized. These complexesconsist of [W6O19]2-and dimeric [Ln2(DNBA)4(DMF)8]2+cations. The luminescenceproperties of14are measured in solid state and different solutions, respectively. Notably,the emission intensity increases gradually with the increase of solvent permittivity, and thissolvent effect can be directly observed by electrospray mass spectrometry (ESI–MS).[La2(DNBA)4(DMF)8][W6O19](11)[Ce2(DNBA)4(DMF)8][W6O19](12)[Sm2(DNBA)4(DMF)8][W6O19](13)[Eu2(DNBA)4(DMF)8][W6O19](14)[Gd2(DNBA)4(DMF)8][W6O19](15)

引文

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