Syntheses,Structures, Fluorescence and Magnetism of Six Lanthanide Metal-organic Frameworks Based on Silicon-centered Tetrahedral Ligand

Multifunctional lanthanide metal-organic frameworks(MOFs), M(H₄TCPS)(H₂O)_1.5[M=Tb(JUC-95a), Er(JUC-95b), Dy(JUC-95c), Tm(JUC-95d), Y(JUC-95e) and Pr(JUC-95f); H₄TCPS=tetrakis(4-carboxyphenyl)silane] were synthesized via the reaction of the lanthanide metal ions(Ln₃?) with a rigid silicon-centered tetrahedral carbo- xylate ligand H₄TCPS via a hydrothermal synthesis method. X-Ray diffraction(XRD) analyses reveal that they are extremely similar in structure and crystallized in a monoclinic system with space group C2/c. Two eight-coordinated metal centers and four tetrahedral H₄TCPS groups constructed a paddle-wheel building block. The paddle-wheel buil- ding blocks assembled with each other via one oxygen bridge from a water molecule to lead to a 1D infinite inorganic rod-shaped chain, -Y-O-C-O-Y-, along the [001] direction. These 1D inorganic rod-shaped chains linked with the phenyl groups of the tetrahedral H₄TCPS ligand to form a 3D framework. In addition, the luminescent and magnetic properties of these compounds show that they could be potential antiferromagnetic and fluorescent materials.     

两个三维柱层式Ce混合羧酸多孔金属-有机骨架配合物的合成、结构与磁性

采用水热法合成了两个新的混合羧酸铈多孔金属-有机骨架配合物[Ce2(fum)3 (H2O)4?(bdc)?(H2O)2]n（1）和[Ce2(suc)2(ox)(H2O)4?(H2O)4]n（2）,利用元素分析、红外光谱、热重分析和单晶X射线衍射对其组成和结构进行了表征,并通过磁性测量研究了其磁学性能. 单晶X射线衍射结果表明,配合物1和2均为三维柱层式多孔金属-有机骨架结构. 配合物1由Ce离子和富马酸（fumarate, fum）形成层,层与层之间再通过富马酸作为柱状配体支撑形成三维结构,并在层间的两个方向上形成相互交错的通道,未配位的中性对苯二甲酸分子（p-benzenedicarboxylate, bdc）和晶格水分子填充于孔道中. 与配合物1类似,配合物2由Ce离子和丁二酸（succinate, suc）形成层,层间通过草酸（oxalate, ox）作为柱状配体支撑形成三维结构,在层间的三个方向上具有相互交错的通道,晶格水分子填充于孔道中.     

Assembly of Two Isostructural Metal-organic Frameworks Based on Hetero-N,O Donor Ligand for Detecting Nitro Explosives

Two isostructural metal-organic frameworks,[NO3][M3(H2O)3O(TBA)3]-2DMF-6H2O(1 and 2)[M=In and Fe, H2TBA=4-(1H-tetrazol-5-yl)-benzoic acid], have been successfully synthesized. Compounds 1 and 2 have three-dimensional structures bridged via the typical 6-connected tri-nuclear cluster units M3O(COO)6 and linear linker H2TBA. The whole 3D framework possesses a 6-connected acs topology. Notably, by the fluorescence technique, compound 1 can detect nitro explosives through fluorescence quenching effect, especially for 2,4,6-trinitrophenol(TNP, Ksv=3.64×10^4 L/mol). Furthermore, the fluorescence spectrum red shifts as the number of NO2 group increases. Based on the aforementioned consideration, compound 1 can be considered as a potential luminescent probe for the detection of TNP.     

Synthesis,Structures and Properties of Three New Compounds Based on Multidentate Ligand Containing Triazole and Pyrimidine

Three new compounds, namely, [Zn(mtpo)₂(H₂O)4](1), [Cd(mtpo)₂·CH₃CH₂OH]_n(2) and [Mn(mtpo)₂·CH₃CH₂OH]_n(3)(Hmtpo=4,7-dihydro-5-methyl-7-oxo-[1,2,4]triazolo[1,5-a]pyrimidine), have been synthesized via hydrothermal or solvothermal methods and characterized by means of elemental analyses, Fourier transform infrared(FTIR) spectroscopy, powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and single-crystal X-ray diffraction. The results obtained from the single-crystal X-ray diffraction indicate that compound 1 has a mononuclear structure, and crystallizes in a monoclinic crystal system with P2₁/c space group, which exhibits a 2D supramolecular network constructed by hydrogen bonds and π-π interactions. Compounds 2 and 3 are isomorphous and crystallize in a tetragonal system with space group of I4₁/a. The M²⁺(M=Cd, Mn) ions in compounds 2 and 3 have the octahedral coordination geometry. Hmtpo acts as a bridging ligand linking the metal ions to form an infinite 3D framework with 4-connected {4²·8⁴} topology. There are hydrogen bonds between the guest ethanol molecules and the mtpoligands, which make the ethanol molecules exist in a 3D framework. In addition, luminescent properties of compounds 1 and 2 as well as magnetic property of compound 3 were investigated and water vapor adsorption and nitrogen sorption for compounds 2 and 3 were researched at 298 and 77 K, respectively.     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性质(英文)

以1,3-二(4′-羧基苯氧基)苯甲酸(H3L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd2(CH3COO)(L)(H2O)2]n(1)和[Na(H2L)]n(2)。由于H3L配体配位模式的不同,配合物表现出不同的网络结构。单晶结构分析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,C2/c空间群。配合物1中Cd2+离子的次级构筑单元经由L3-连接形成三维网络结构。配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(46·64)。此外,还对配合物1的荧光性能进行了分析。     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性

以1,3-二(4'-羧基苯氧基)苯甲酸(H₃L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd₂(CH₃COO)(L)(H₂O)₂]_n (1)和[Na(H₂L)]_n (2).由于H₃L配体配位模式的不同,配合物表现出不同的网络结构.单晶结构分析表明,配合物1属于三斜晶系,P1 空间群,配合物2属于单斜晶系,C2/c空间群.配合物1中Cd₂₊离子的次级构筑单元经由L^3-连接形成三维网络结构.配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(4⁶·6⁴).此外,还对配合物1的荧光性能进行了分析.     

基于金属卟啉2DMOFs仿酶催化的过氧化氢比色法检测

以四(4-羧苯基)铁卟啉(FeTCPP)作为有机配体,铜离子作为金属节点,利用溶剂热法制备了双金属Cu-FeTCPP金属有机骨架(MOFs)材料,并采用表面活性剂辅助法合成了二维纳米片(Cu-FeTCPP 2DMOFs).该纳米片呈超薄的纳米结构,与三维块体结构(3DMOFs)相比具有更大的比表面积.基于Cu-FeTCPP 2DMOFs的仿酶特性,将其用于催化过氧化氢(H₂O₂)氧化底物3,3′,5,5′-四甲基联苯胺(TMB)显色,根据显色产物吸光度与H₂O₂浓度之间的正比关系实现了对H₂O₂的测定.经稳态动力学分析发现,底物相同时该纳米片的米氏常数K_m均比Cu-FeTCPP 3DMOFs的K_m小,表明纳米片与底物之间有更好的亲和力,这归因于二维结构大的比表面积和较多易接近的活性位点.基于Cu-FeTCPP 2DMOFs构建的比色检测方法在优化条件下对H₂O₂的线性检...     

2个新颖的(3,4,6)和(3,6)连接的多核金属有机骨架化合物的合成、结构与性质

在水热和溶剂热条件下合成了2个新颖的金属有机骨架化合物{[Cu_3(BCPBA)_2(bpmp)(H_2O)]·2DMF}n(1)和{Zn3(BCPBA)_2(bip)(H_2O)_2}n(2)[H3BCPBA=3,5-双(4-羧基-苯氧基)苯甲酸;bpmp=1,4-二(吡啶-4-亚甲基)哌嗪;bip=1,3-二(咪唑基)丙烷].通过单晶及粉末X射线衍射、红外光谱、元素分析和热重分析对这2个化合物进行了表征.结果表明,化合物1属于单斜晶系,C2/m空间群,是由羧酸连接3个二级结构单元[Cu_2(CO_2)4]形成的具有自穿插结构的三维骨架结构,其骨架拓扑符号为(4·8~2)(8~6)(4~2·6~8·8~3·9·10);化合物2属于三斜晶系,P1空间群,其骨架是由1个新颖的二级结构单元组成的拓扑结构为(4~2·6)_2(4~4·6~2·8~8·10)的三维超分子网络.     

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.     

Synthesis,Structures and Properties of Two Complexes Based on Benzimidazole or Benzothiazole Ligand

Two complexes,Co（Hbim）2（NCS）2（Hbim=benzimidazole）（1） and [Cu（Hbzt）SCN]n（Hbzt=benzothiazole） （2） were synthesized by the same synthesis method and characterized by elemental analysis,infrared spectroscopy（IR）,thermogravimetric analysis（TGA）,X-ray powder diffraction（XRPD） and single-crystal X-ray diffraction.The results from the single-crystal X-ray diffraction indicate that complex 1 is zero-dimensional（0D） framework and complex 2 is 2-dimensional（2D） framework.In complex 2,the 3-dimensional（3D） supermolecular architecture was built up by means of π-π stacking interaction,and two helical chains existed in its structure.The luminescence properties and the magnetic properties of the two complexes were investigated.     

A Luminescent Metal-Organic Framework with LON Topology for Highly Effective Fluorescence Sensing of Fe3+ and TNP

Aluminescent Ag-based metal-organic framework(1) has been synthesized and its structure has been characterized. Compound 1 was fabricated using the Ag⁺ and bbimb^2‒ ligands and manifestes a rare LON topology. Compound 1 is selective not only in detecting traces of Fe³⁺ and 2,4,6-trinitrophenol(TNP) via luminescence quenching, but also demonstrates high selectivity in the presence of other competitors. Compound 1’s K_sv values towards Fe³⁺ can reach as high as 9.3×10³ L/mol, which is higher than those of several other MOF materials. It is also a recyclable luminous sensor with the potential to be utilized for detecting TNP. Hence, based on its characteristics, compound 1 can be regarded as a prospective luminescence sensor for detecting Fe³⁺ and TNP.     

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.     

具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征

在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni₂L₂(bpy)]_n(2)和{[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3)[H₂L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{4²·6⁵·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{4⁸·5⁴·6³}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P\begin{array}{c}\bar{1}\end{array}空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{4⁴·6²}拓扑结构.     

Syntheses,Structures and Magnetic Properties of Two Coordination Polymers Based on 2, 2-Biphenyldicarboxylate Ligand

Two coordination polymers {[Co₃L₃(Me₂NH)₂]·(Me₂NH)}_n(1) and [CuL(bpy)]_n(2)(L=2,2'-biphenyl dicarboxylate ion, bpy=4,4'-bipyridine) were obtained and characterized. Compound 1 was synthesised via solvothermal method, with the L ligands adopting syn-syn-μ₂-η¹:η¹- and μ₂-η²-coordination modes and Co(II) centers being linked to form a 1D coordination chain with trinuclear Co₃ cluster as sub-units. Compound 2 was synthesized at room temperature, with the L ligand chelating the Cu(II) centers to form a 1D chain, which was further linked by the auxiliary 4,4'-bpy ligand to form a 3D coordination network. The results of variable temperature susceptibility studies reveal that there were ferromagnetic and antiferromagnetic interactions between the paramagnetic metal centers in compounds 1 and 2, respectively.     

两个基于四面体型配体的镉配合物的合成、晶体结构及性质

用四面体构型的配体四[3-(羧基苯)氧甲基]甲烷(H₄L)与镉离子通过溶剂热法合成了结构不同的配合物[Cd₆L₃(DMA)₃(H₂O)]_n(1)和{[Cd₂L(H₂O)₄]·4H₂O}_n(2)(L=四[3-(羧基苯)氧甲基]甲烷)。化合物1属于三方晶系R3空间群。每个配体通过4个羧基连接了4个三核镉簇,每个三核镉簇连接了6个苯甲酸,形成双节点(4,6)-连接toc拓扑构型的三维骨架结构。配合物2属于单斜晶系C2/c空间群。每个配体连接了4个镉原子,仍保持四面体构型。镉原子由羧基沿着b轴连接成一维链,链与链之间通过配体连接,且2个相邻配体的苯环之间存在π-π堆积。此外,对化合物1和2在室温下做了固态紫外和荧光性质的研究。     

两个基于四面体型配体的镉配合物的合成、晶体结构及性质

用四面体构型的配体四[3-(羧基苯)氧甲基]甲烷(H₄L)与镉离子通过溶剂热法合成了结构不同的配合物[Cd₆L₃(DMA)₃(H₂O)]_n (1)和{[Cd₂L(H₂O)₄]·4H₂O}_n (2)(L=四[3-(羧基苯)氧甲基]甲烷)。化合物1属于三方晶系R3 空间群。每个配体通过4个羧基连接了4个三核镉簇, 每个三核镉簇连接了6个苯甲酸, 形成双节点(4, 6)-连接toc拓扑构型的三维骨架结构。配合物2属于单斜晶系C2/c空间群。每个配体连接了4个镉原子, 仍保持四面体构型。镉原子由羧基沿着b轴连接成一维链, 链与链之间通过配体连接, 且2个相邻配体的苯环之间存在π-π堆积。此外, 对化合物1和2在室温下做了固态紫外和荧光性质的研究。     

Synthesis,Structures, Luminescence,and Magnetic Properties of Two Three‐dimensional Lanthanide Organic Frameworks Comprising Pyrazine‐2,3‐dicarboxylic Acid

Two three‐dimensional (3D) lanthanide coordination polymers (CPs) of the general formula [Ln₂(PDOA)₃(H₂O)]_n · 2nH₂O [Ln = Gd ( 1 ), Tb ( 2 )] were synthesized by solvothermal reactions of the corresponding rare‐earth chloride and pyrazine‐2,3‐dicarboxylic acid (H₂PDOA). The CPs were structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, thermogravimetry, and elemental analysis. CPs 1 and 2 are isostructural and crystallize in the monoclinic space group P2₁/c. The frameworks are constructed from dinuclear lanthanide building blocks in which the PDOA^2– ions adopt three coordination modes, μ₃‐kO;kO;kN,O, μ₄‐kN,O;kO;kO;kO,O, and μ₅‐kN,O;kO;kO;kO,O;kO, respectively. The Tb³⁺ polymer of 2 exhibits characteristic photoluminescence in the visible region. The magnetic properties of CP 1 were investigated by measuring the magnetic susceptibilities in the temperature range 1.8–300 K.     

两种新型多孔金属-有机凝胶的合成、表征与气体吸附性能

以1,4-二(3-乙酰丙酮基)苯(DAB)为有机配体分别与铝离子和铬离子反应,合成出2个新型的金属-有机凝胶:Al-湿凝胶和Cr-湿凝胶,通过直接干燥法得到相应的2种多孔干凝胶:Al-干凝胶和Cr-干凝胶.通过X射线粉末衍射仪(PXRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)、热重分析仪(TGA)、X射线能谱仪(EDS)和氮气吸附-脱附仪对凝胶材料的结构和形貌进行了表征.结果显示,2种多孔金属有机凝胶材料是由球状纳米粒子堆积而成,具有较高的比表面积、丰富的微孔及少量的介孔结构.气体吸附性能测试结果表明,Al-干凝胶的比表面积为790.3 m2/g,在1.01×105Pa,77 K下能够吸附117.45 cm3/g的氢气,在273 K下能够吸附60.74 cm3/g的二氧化碳.     

四氮唑衍生物构筑的金刚烷拓扑金属-有机骨架的合成、表征及荧光性质

5-氨基四氮唑(HATZ)与硝酸锌通过溶剂热反应得到了一个新的化合物,[Zn(ATZ)2]?DMA (1),并对其进行了X射线粉末衍射,红外和元素分析表征. 单晶X射线分析表明,该化合物展示了一个三维四连接金刚烷拓扑的微孔金属有机框架,沿[100]方向的孔道维度大约12.7 ? × 8.9 ?,PLATON计算表明孔体积为53.5%. 此外,荧光光谱测试表明化合物在室温下显示较强的蓝色荧光性质.     

Synthesis,Characterization, and Structures of Tetrakis(2-Pyridyl)Tin Compounds

Abstract

Reactions of 2-bromopyridine and 2-bromo-6-methylpyridine with n-BuLi and tin tetrachloride afforded Sn(2-py)₄ (1a) and Sn(6-Me-2-py)₄ (1b), respectively. The identities of the two compounds were unambiguously proved by microanalyses, NMR (¹H, ¹³C, ¹¹⁹Sn) spetroscopy, and single-crystal X-ray diffraction studies.