Synthesis,Crystal Structure and Luminescent/magnetic Properties of Two Metal-organic Frameworks Based on Multi-N/O-donor Mixed Ligands

Two new complexes, namely [Cd_2(L)(pycy)(Cl)]·2 H_2 O(1) and [Cu(HL)(H_2 btac)]·2 H_2 O, have been synthesized by the reaction of the corresponding metal salts with mixed ligands including 1-(1 H-imidazol-4-yl)-4-(4 H-tetrazol-5-yl)benzene(HL), 2,6-pyridinedicarboxylic acid(H2 pycy) and 1,2,4,5-benzenetetracarboxylic acid(H4 btac), and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and powder X-ray diffraction(PXRD). Complex 1 crystallizes in triclinic, space group P■ with a = 9.8938(7), b = 10.1662(7), c = 12.4520(8) ?, α = 92.7070(10), β = 108.1310(10), γ = 105.3230(10)°, V = 1136.44(13) ?3, Z = 2, C17 H12 N7 O6 Cl Cd2, Mr = 670.59, Dc = 1.960 g/cm3, μ = 2.037 mm-1, S = 1.062, F(000) = 648, the final R = 0.0532 and w R = 0.1651 for 12156 observed reflections(I 2σ(I)). Complex 2 crystallizes in triclinic, space group P■ with a = 7.3058(8), b = 7.4890(8), c = 10.8937(12) ?, α = 71.3810(10), β = 84.134(2), γ = 65.745(2)°, V = 514.68(10) ?3, Z = 1, C_(20) H_(16) Cu N6 O10, M_r = 563.94, D_c = 1.819 g/cm~3, μ = 1.139 mm-1, S = 1.187, F(000) = 287, the final R = 0.0314 and w R = 0.0807 for 3564 observed reflections(I 2σ(I)). Single-crystal X-ray structural analysis reveals that complex 1 features a trinodal(3,3,4)-connected two-dimensional(2 D) net layer with Schl?fli symbol(4·6·8)(4·6~2·8~3)(6~2·8) while 2 has a 2 D network with 4~4 sql topology. Moreover, the photoluminescent property of 1 and magnetic property of 2 were also discussed.     

基于杂环羧酸配体的金属有机骨架化合物合成、表征及性质研究

以噻吩-2,5-二羧酸为主要配体,借助第二配体----4,4-联吡啶或者邻菲罗啉通过水热法合成了三种MOFs材料,分别是[Cd (tdc) (bpy)]n、[Zn (tdc) (bpy)]n、[Co (tdc) (phen)]n。利用X射线单晶衍射仪、红外光谱仪对三种MOFs材料进行了结构表征与分析,同时利用荧光光谱仪、热重分析仪和电化学工作站测定了三种MOFs材料的荧光性质、热稳定性和MOFs材料修饰玻碳电极的电化学行为,结果表明,三种MOFs材料比配体更好的荧光强度和热稳定性,制备的[Co (tdc) (phen)]n修饰玻碳电极,对铁氰化钾溶液和含1.0mmol/L NaNO2的pH = 5 PBS溶液,均比裸玻碳电极表现出更强的循环伏安响应,有望作为修饰剂应用于修饰玻碳电极中。     

C3对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质

以稀土离子(La,Ce,Pr,Nd)与具有C3对称结构的芳香羧酸配体N,N’,N″-三(4-苯甲酸基)-1,3,5-苯三甲酰胺(BTMC)为构筑单元,合成了4个同构的三维非穿插金属-有机骨架化合物[Ln(BTMC)(DMF)]·3H2O·2.5DMF[Ln=La(1),Ce(2),Pr(3),Nd(4)].采用单晶X射线衍射、粉末X射线衍射(PXRD)、红外光谱和热重分析对其结构及稳定性进行了表征,并测试了它们捕获不同金属离子(La3+,Ce3+,Pr3+,Nd3+,Cd2+,Cr3+,Cu2+)及吸附染料甲基橙和曙红的固态荧光光谱变化.结果表明,化合物对金属离子及染料均有一定吸附作用,捕获Cr3+后荧光强度变化最大,说明对Cr3+具有较好的识别作用.     

金属有机框架与新型载药体系

金属-有机骨架材料(MOFs)是一类由金属离子与有机配体之间的配位自组装形成的新型多孔复合材料。因其具有高比表面积、可调的尺寸、拓扑结构多样性、合成简便、有机基团易于功能化等优点使其在生物分析、成像、传感、催化、气体存储与分离以及药物运载等领域具有广泛的应用前景。这里通过简要介绍MOFs的研究背景,基于MOFs孔径的药物装载策略以及MOFs药物释放的刺激响应方式,阐述MOFs作为药物递送载体的最新进展,为后期药物载体的设计提供参考。     

Two New Cadmium Metal-organic Frameworks Based on a Mixed-donor Ligand

The self-assembly of a prominent mixed-donor ligand, 5-[4-(1H-tetrazolyl)phen]isophthalic acid(H₃TZPI), with a Cd²⁺ center generates two new metal-organic frameworks:[Cd(H₂TZPI)₂(H₂O)₂]_n(JUC-163) and[Cd₂(TZPI)(μ₃-OH)(H₂O)₂]·H₂O·DMF(JUC-164). The two complexes demonstrate different structures for the ligand’s different coordination modes and configurations. JUC-163 shows a 2D layer structure and further forms into a 3D supramolecular framework by noncovalent interactions(C-H…O, O-H…N and π…π interactions), whereas JUC-164 exhibits a fascinating 3D framework for the outstanding coordination modes and configurations of the ligand, which are fit for the complex structure. And also, the factor of different cadmium salts(chloride and nitrate) which are used in synthesis progress is worth to notice for the construction of the two distinct structures. The luminescent properties of these metal-organic frameworks were also investigated.     

水稳定性金属有机框架材料的水吸附性质与应用

金属有机框架材料(metal-organicframeworks,MOFs)因具有高比表面积、高孔隙率以及可调的孔结构及孔内环境,在气体吸附、分离以及催化等方面展现出巨大应用潜力.由于水蒸气广泛存在于空气和各类工业气体中,深入理解MOFs与水蒸气之间相互作用机制,并开发具备高水稳定性以及水蒸气吸附与脱附行为可调的MOFs,不仅具有显著的科学意义,而且对推动MOFs的实际应用具有重要的现实意义.本综述将围绕以下内容展开论述:高水稳定性MOFs的设计规律;MOFs对水蒸气的吸附/脱附行为;吸水MOFs在工业气体干燥、沙漠取水、吸附式热泵以及室内湿度调节等领域的应用.     

Syntheses,Structures,Luminescence and Magnetic Properties of Three New Metal-organic Frameworks Based on Rigid Carbazole Ligand

Three new metal-organic frameworks [Cd(L)(obba)]·H)2O(1),[Co(L)(obba)]·MeCN(2) and [Cd_2(L)_2(ip)_2]·6H_2O·DMF(3)(H_2obba = 4,4?-oxybisbenzoic acid,H2 ip = m-phthalic acid) have been successfully synthesized based on the controllable self-assembly of 9-ethyl-3,6-diimidazolyl-carbazole(L),varied carboxylates and different metal ions under solvothermal conditions,which were characterized by single-crystal X-ray diffraction,elemental analysis,IR spectroscopy and thermogravimetry. Furthermore,luminescence and magnetic susceptibility of compound 2 are also investigated in detail. Single-crystal X-ray diffraction and topology analysis reveal that complexes 1~3 exhibit similar two-dimensional(2D) networks.     

咪唑二羧酸构筑的铕配合物的合成、晶体结构及发光性能

2-(邻溴)苯基-4,5-咪唑二羧酸(o-BrPhH₃IDC)与六水合硝酸铕(Eu(NO₃)₃·6H₂O)在对苯二甲酸存在下,在乙睛和水的混合溶剂中,通过溶剂热反应,合成了一个三维超分子配合物(H₃O)[Eu(o-BrPhH₂IDC)₄](1)。 采用单晶X射线衍射对配合物1的晶体结构进行了测试,结果表明,配合物1为立方晶系,I-43d空间群;中心铕离子处于一个八配位的体系中。 对配合物1的固态荧光研究发现:在395 nm的激发波长下,标题配合物显示出特征的铕发射光谱。 这说明所采用的有机配体具有良好的天线效应,对铕离子有很好的敏化效应。     

Luminescent Properties of Some Rare Earth Phosphates

Abstract

Luminescent properties of scandium and yttrium phosphates are discussed and mechanisms involving their emissions proposed.     

Synthesis and Detection of Pesticides of Luminescent Metal-organic Framework Based on Carboxyl-decorating Tetraphenylethylene

A water-stable porous anionic metal-organic framework(MOF), [(CH_3)_2NH_2][In(TCPP)_(4/3)]_n·(2DMF)_n(3H_2O)_n(1, TCPP = 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene), was synthesized. Here, compound 1 showed extremely high sensitivity and selectivity to current general-purpose pesticide 2,6-dichloro-4-nitroaniline(DCN) in aqueous solution. The fluorescence intensity of compound 1 could be decreased as much as 80% by 6 mL DCN, and it was almost completely quenched only with 20 mL DCN. The results indicate that compound 1 can act as a fluorescent probe for DCN.     

异核稀土双亚砜配合物的合成、表征和荧光性质

合成得到一系列异核土双乙烷配合物和异核稀土双乙烷与１,１０－啡咯啉的配合物,通过元素分析,电感耦合等离子体法,电导,红外和紫外光谱对配合进行了表征,并研究了这些配合物的固体和溶液的荧光光谱。     

二维金属有机框架材料的合成及电催化应用

二维金属有机框架材料(MOFs)由于具备高比表面积、 多孔性以及丰富的活性位点等优异特性而受到广泛关注, 并且在电催化领域展现出巨大的应用潜力. 研究者们已在二维MOFs的可控制备与电催化性能调控方面取得许多突破性进展, 显示出相关研究对开发高性能电催化剂的关键作用. 本文总结了二维MOFs的自上而下和自下而上合成策略以及二维MOFs衍生物的典型合成方法, 概述了二维MOFs在各尺度下的电催化性能调控策略, 并介绍了各种合成方法和调控策略在电催化中的应用. 最后讨论了该领域面临的挑战, 并对未来的发展方向进行了展望.     

多孔金属有机框架的组装与性能研究进展

对多孔金属有机框架的组装及其对气体的吸附性能的研究进展进行了评述,并对磁性和手性多孔金属有机框架进行了介绍.     

具有三核Cd(Ⅱ)簇单元和螺旋链的脯氨酸类单一手性金属-有机框架材料的合成、 结构和性质

在溶剂热反应条件下, 使用含氮辅助配体1,4-二(4-吡啶基)苯(1,4-DPB)和半刚性脯氨酸衍生物配体(R)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(R)-H₃PIA]或(S)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(S)-H₃PIA]与Cd²⁺构筑了单一手性金属-有机框架材料[Cd_1.5((R)-PIA)(1,4-DPB)_1.5]·0.75H₂O·xGuest(1-D)和[Cd_1.5((S)-PIA)(1,4-DPB)_1.5]·0.75 H₂O·xGuest(1-L). 配合物1-D和1-L呈具有开放孔道的三维柱层式框架结构, 含有三核镉簇单元 Cd₃(CO₂)₆与两种螺旋链构建的波浪形Cd-PIA层. 分别对上述化合物进行了粉末X射线衍射、 热重分析、 圆二色谱和荧光光谱等测试. 测试结果显示配合物1-D和1-L都是以纯晶体的形式存在, 2种配合物的热失重曲线接近, 圆二色谱有明显的正负吸收峰, 符合其对映体的结构特征.     

新型吡唑啉酮稀土配合物的合成及荧光性能

通过分子设计,以吡啶-2,6-二甲酸为起始原料,合成了一种新型双吡唑啉酮吡啶配体:2,6-二(1-苯基4-乙氧羰基-5-吡唑啉酮-3-基)吡啶(H2L)。配体与稀土Eu(Ⅲ)和Tb(Ⅲ)离子成功螯合形成配合物。配体和配合物经FT-IR,1H NMR和元素分析进行表征,并确定配合物组成为RE2L3.4H2O。对配合物的紫外吸收和光致发光性能进行了检测,结果显示Eu(Ⅲ)和Tb(Ⅲ)离子能够有效地被有机配体敏化,发射出高亮、半峰宽狭窄的单色光。研究表明目标配合物能够成为优秀的发光材料。     

Structural Modulation of Two Luminescent Bismuth-organic Frameworks by the Mixed-ligand Synthetic Strategy

Hydrothermal reactions of Bi_2O_3 with pyridine-2,6-dicarboxylic acid(2,6-H_2pdc) and trimesic acid(H3btc)/pyromellitic acid(H4pyr) lead to two bismuth-organic frameworks, namely, [Bi(2,6-pdc)(H_2btc)(H_2O)2]n(1) and [Bi_2(2,6-pdc)2(H2pyr)(H_2O)_2]n(2). Compound 1 crystallizes in the space group P2_1/c. The dimeric {Bi_2} units are linked by 2,6-pdc2-ligands to form 1D chains; Compound 2 exhibits a 2D layered structure with 44 network topology by using dimeric {Bi_2} as secondary building units(SBUs). The chains and layers in 1 and 2 are further arranged into 3D supramolecular structures via hydrogen bonding interactions. The compounds emit blue luminescence. Furthermore, the PXRD, TGA, UV-visible and IR spectra were also studied. Compounds 1, 2 represent good examples of using mixed-ligand approach to construct diversity of luminescent bismuth-organic frameworks.     

金属有机骨架材料/聚酰亚胺混合基质膜的制备及气体分离性能

合成了3种不同结构、 粒径和气体吸附性能的金属有机骨架材料(MOFs): 微米级Cu₃(BTC)₂、 亚微米级ZIF-8和S-Cu₃(BTC)₂. 氮气吸附等温线分析结果表明, ZIF-8和Cu₃(BTC)₂具有较大比表面积(1653和1439 m²/g), S-Cu₃(BTC)₂的比表面积为171.4 m²/g. 用共混法将MOFs直接引入聚酰亚胺中制备了MOFs/聚酰亚胺混合基质膜(MMMs). X射线衍射(XRD)和全反射红外光谱(FTIR-ATR)分析结果表明, MOFs在混合基质膜中保持物理和化学稳定. 气体渗透测试结果表明, MOFs的加入使膜的气体渗透分离性能明显提高, S-Cu₃(BTC)₂使渗透系数增加了1.75倍; ZIF-8和Cu₃(BTC)₂使渗透系数增加了3倍左右; 同时, 膜的气体分离系数变化很小.     

互穿结构及混合配体对金属-有机骨架材料分离性能的影响

在以前的工作中, 我们利用蒙特卡洛和分子动力学模拟计算了具有互穿性结构及混合配体的金属-有机骨架材料(metal-organic frameworks, MOFs)分离CH₄/H₂的吸附选择性及扩散选择性. 研究了材料的互穿结构及混合配体对材料用于分离CH₄/H₂性能的影响. 在本工作中, 我们将以前的工作进行了扩展, 详细研究了材料的互穿结构及混合配体对材料用于分离CO₂/CH₄, CO₂/N₂和CO₂/H₂等含有CO₂的气体混合物性能的影响. 此外, 为了进一步阐明材料的结构对于其分离性能的影响, 我们亦研究了材料用于分离CH₄/H₂及CH₄/N₂. 从我们的结果可以看出, 相比无互穿结构的MOFs材料, 具有互穿结构的MOFs材料对所研究的所有混合气体的渗透选择性明显提高. 这是因为具有互穿结构的MOFs材料对混合气体的吸附选择性明显高于无互穿结构的MOFs材料. 结果表明, 如果将材料作为膜用于气体混合物分离, 使材料产生互穿结构是提高材料分离性能的一个很好的策略.