基于2，5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法,以2,5-二溴对苯二甲酸(H₂L)为配体,分别与六水合硝酸钕、六水合硝酸钆反应合成了2种镧系金属有机骨架(MOFs)：{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明,2个配合物均是以稀土离子为金属节点,与配体相互连接,形成无限延伸的三维网状结构。     

基于2,5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法, 以2, 5-二溴对苯二甲酸(H₂L)为配体, 分别与六水合硝酸钕、六水合硝酸钆反应合成了 2种镧系金属有机骨架(MOFs):{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明, 2个配合物均是以稀土离子为金属节点, 与配体相互连接, 形成无限延伸的三维网状结构。     

基于3，4'，5-联苯三羧酸构筑的钕配合物的合成、结构、荧光、光催化及磁性质

采用NdCl₃·6H₂O和3,4'',5-联苯三羧酸（H₃bpt）为原料在DMF/H₂O混合溶剂热条件下合成得到一个三维钕配合物{[Nd （bpt）（DMF）（H₂O）]·2H₂O}_n（1）,并通过红外光谱、元素分析、单晶及粉末X射线衍射表征了配合物1的结构。单晶衍射结果表明,配合物1具有（5,5）-连接的三维结构,拓扑符号为（4⁴·6³·8³）（4⁸ 6²）。此外,对配合物1的热稳定性、荧光性质、光催化降解染料及磁性质进行了详细研究。     

有机-无机杂化配位聚合物{[C12H28N2][(Pb3I8) (DMF)2]•2DMF}n的晶体及电子结构

合成了一种新颖有机-无机杂化配位聚合物{[C₁₂H₂₈N₂] [(Pb₃I₈)(DMF)₂]•2DMF}_n, 并进行了红外、紫外、热重表征, 采用X射线衍射方法确定了晶体结构. 结构解析表明, 整个分子由阳离子(双质子化的N,N'-二丁基哌嗪)及聚阴离子链([(Pb₃I₈)(DMF)₂]_n^2-)组成, 它们之间由静电作用结合在一起形成一维链状配位聚合物. 依据晶体结构数据, 采用Gaussian03程序对产物进行量子化学计算.     

Potassium carbazolyl complexes with coordinating solvents: Syntheses and crystal structures

The reaction of carbazole with KOH in dimethylformamide (DMF) at 75°C for 1.5 h affords CarbK(DMF) (CarbH is carbazole) in 90% yield. The crystallization of the compound from DME, CH₃CN, and CD₃CN gives complexes CarbK(DME)₂, CarbK(DMF)(CH₃CN), and CarbK(DMF)(CD₃CN), respectively, whose structures are determined by X-ray diffraction analyses. The dissolution of CarbK(DMF)(CH₃CN) in CD₃CN results in the deuterium exchange in the bound solvent to form complex CarbK(DMF)_0.5(CD₂HCN)_1.5, whose structure is also established by X-ray diffraction analysis.     

Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures

Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials.     

Synthesis,crystal structures,and magnetic properties of three isomorphous helical coordination polymers

Three isomorphous coordination polymers of general formula {[M(H₂bna)·(DMF)₂·(H₂O)₂]·DMF}_n (M = Co for 1, Mn for 2, Ni for 3, respectively, where H₄bna = 2,2′-dihydroxy-[1,1′]-binaphthalene-3,3′-dicarboxylate) were synthesized under solvothermal conditions and characterized by FTIR, single crystal X-ray diffraction, thermogravimetric analysis, and X-ray power diffraction analysis. All three polymers crystallize in the same monoclinic space group P2₁/n. The complexes are assembled into 1D helical chains, and each adjacent helical chain of the same chirality is further connected to form a chiral layer by hydrogen bond interactions. The layers are packed in alternating left-(M) and right-handed (P) chirality arrays. Magnetic studies reveal the presence of antiferromagnetic coupling interactions in complexes 1 and 2.     

柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质

利用2,2''-(1,4-亚苯基)二(亚苯基)二(硫基)苯二羧酸(H₂L¹)和2,2''-(2,3,5,6-四甲基-1,4-亚苯基)二(亚甲基)二(硫基)苯二甲酸(H₂L²)2个柔性二羧酸分别与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物:{[(NH₂(CH₃)₂][Nd(L¹)₂(DMF)]·2DMF}_n(1)和{[Ln(L²)_1.5(H₂O)(DMF)₂]·2DMF}_n[Ln=Ce(2),Pr(3)]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明:3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。(L¹)^2-在配合物1中表现出顺式和反式2种构象,(L2²)^2-在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质

利用2,2''-（1,4-亚苯基）二（亚苯基）二（硫基）苯二羧酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）二（亚甲基）二（硫基）苯二甲酸（H₂L²）2个柔性二羧酸分别与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[（NH₂（CH₃）₂][Nd（L¹）₂（DMF）]·2DMF}_n（1）和{[Ln（L²）_1.5（H₂O）（DMF）₂]·2DMF}_n[Ln=Ce（2）,Pr（3）]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明：3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。（L¹）^2-在配合物1中表现出顺式和反式2种构象,（L²）^2-在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

Hydrothermal syntheses and crystal structure of a novel one-dimensional Pb(II) coordination polymer with chenodeoxycholic acid ligand

A novel 1D chain-like coordination polymer, {[Pb(CDCA)₂(DMF)] · DMF · 2H₂O]} _n (I) (HCDCA = chenodeoxycholic acid, DMF = dimethyl formamide), has been synthesized by hydrothermal method and characterized by single crystal X-ray diffraction, IR spectroscopy, and elemental analysis (CIF file CCDC no. 996098). X-ray diffraction analyses indicated that I displays distorted octahedral metal centers with secondary building units [Pb(CDCA)₂(DMF)] bridged by a pair of μ²-COO^?-bridges. In the crystal, interchain O-H?O hydrogen bonds are present and assemble the neighboring 1D chain into a (4,4) sql type three-dimensional (3D) supramolecular topological network.     

基于2-硫代巴比妥酸构筑零维原子簇{[Cu6(H2tba)6]·2DMF·xSolvent}、二维层状{[Sc(H2tba)3(DMF)]·2DMF}n和三维网状{[Fe(H2tba)2(H2O)2]·2DMF}n

分别以Cu (ClO₄)₂·6H₂O、Sc (ClO₄)₃·6H₂O和Fe (ClO₄)₃·9H₂O为金属盐,2-硫代巴比妥酸(H₃tba)为配体,通过扩散反应得到了3种不同结构的配合物{[Cu₆(H₂tba)₆]·2DMF·xSolvent}(1)、{[Sc (H₂tba)₃(DMF)]·2DMF}_n(2)和[Fe (H₂tba)₂(H₂O)₂]_n(3),并用红外光谱、元素分析、热重分析和粉末X射线衍射对配合物进行了表征。单晶X射线衍射结构分析表明配合物1是一个具有三方反棱柱构型的六核铜原子簇合物,配合物2是一个具有二维层状结构的化合物,配合物3是一个具有三维网状结构的配位聚合物。配合物1在390 nm光照激发下在735 nm处有强的荧光发射峰。     

席夫碱三核锌(II)配合物的晶体结构及荧光活性研究

以二甲基甲酰胺(DMF)为溶剂成功合成了水杨醛缩水杨酰肼席夫碱/2-氨基吡啶/锌三元混配配合物晶体, 通过测定配合物的红外、元素分析和单晶衍射等物理性质, 确定该配合物是一种三核配合物. Ｘ射线衍射实验结果表明: 标题配合物晶体属于三斜晶系, 空间群为P1, Z＝1, 分子式为Zn₃(L1)₂(2-NH₂-py)₄•0.5DMF, a＝1.15359(9) nm, b＝1.92734(15) nm, c＝2.31772(19) nm, α＝78.290(2)°, β＝78.6930(10)°, γ＝88.1090(10)°, V＝4.9478(7) nm³, D_c＝1.498 g/cm³. F(000)＝2288, μ(Mo Kα)＝1.506 mm^－1, R＝0.0449, wR＝0.0787. 同时在DMF溶液中测定了该Schiff碱及其锌配合物的荧光活性.     

A pillar-layered Cd(II) metal-organic framework for selective detection of organic explosives

The detection of explosives is crucial for homeland security, environmental cleaning, and military issues. As a new class of porous materials, metal-organic frameworks (MOFs) are promising platforms for the detection of organic explosives. In this work, a new pillar-layered Cd(II) MOF, [CdL_0.5dpe_0.5]·2H₂O (BUT-202, H₄L = 4,8-disulfonaphthalene-2,6-dicarboxylic acid, dpe = 1,2-bis(4-pyridyl)ethylene), was synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and elemental analysis. BUT-202 has good fluorescent properties, which can be selectively quenched by trace amounts of 2,4,6-trinitrophenol (TNP) in DMF with low detection limit of 0.2 μM.     

基于2,5-噻吩二甲酸的钙(Ⅱ)和钡(Ⅱ)配位聚合物的合成、晶体结构及性质

在溶剂热条件下,合成了2个碱土金属配位聚合物[Ca（tdc）（DMF）₂]_n（1）和[Ba（tdc）]_n（2）（H₂tdc=2,5-噻吩二甲酸）,分别用元素分析、红外光谱、X射线单晶衍射、粉末衍射、热重分析和荧光光谱对它们进行了表征。结构分析表明,配合物1具有4,4连接的二维层状结构,拓扑符号为（4⁴·6²）,而配合物2呈现三维网络结构。固体荧光测试表明配合物1比配合物2具有更显著的荧光性能。     

Syntheses,crystal structures,and thermal stabilities of the first Hofmann-DMF-type complexes Zn(DMF)2M(CN)4 (M = Ni,Pd, Pt)

The first Hofmann-DMF-type complexes Zn(DMF)₂M(CN)₄ (M = Ni (1), Pd (2), Pt (3)) have been synthesized by solution diffusion and characterized structurally by single-crystal X-ray diffraction. The structure consists of 2-D corrugated sheets stacking along the a-axis in an ABAB packing mode without interpenetration. The octahedral Zn ions and square-planar M ions occupy special positions of 2/m site symmetry. The DMF, except for six methyl H atoms, lies on a crystallographic mirror plane; the DMF molecules coordinate to axial sites of Zn on both sides of the sheet. The framework of 1 begins to collapse with loss of coordinated DMF.     

Two chiral cadmium carboxylate framework isomers generated by spontaneous resolution: synthesis,structures and properties

Two three-dimensional (3-D) chiral coordination polymers, [Cd(NDC)(DMF)]_n (1_L and 1_D: H₂NDC = 1,4-naphthalenedicarboxylic acid and DMF = N,N′-dimethylformamide), have been synthesized by introducing the rigid achiral dicarboxylic acid ligand under solvo-thermal conditions, without chiral template or additives. Both chiral Cd-CPs were characterized by single crystal X-ray crystallography, and structural analysis indicates that 1_L and 1_D are enantiomers based on the zigzag [Cd(COO)₂(DMF)]_n rod secondary building units, featuring the left- or right-hand 2₁ Cd-O-C-O-Cd helix chains and left- or right-hand 4₁ screw [Cd(NDC)]_n columns, respectively. The FT-IR, TGA, powder X-ray diffraction and solid-state luminescence of 1 have been investigated. It is intriguing that the evidence from the circular dichroism spectroscopies confirms enantiomeric excess in the whole spontaneous resolution crystallization.     

A novel 3D supramolecular coordination polymer based on tetranuclear complex of lead(ii) with terephthalic acid and 8-hydroxyquinolin, [Pb4(8-Quin)4(Tp)2(DMF)2] n

A novel two-dimensional coordination polymer, [Pb₄(8-Quin)₄(Tp)₂(DMF)₂] _n (Tp = terephthalic dianion, 8-Quin = 8-Hydroxyquinolate, and DMF = N,N-dimethylformamide) has been synthesized and characterized by elemental analysis, FT-IR, and single crystal X-ray diffraction. The single crystal X-ray analysis shows that the complex is a two-dimensional (2D) polymer and the dimensionality is further increased to 3D as a result of weak C-H???? and C-H??O interactions.     

An ion crystal based on MnII-Schiff-base and Keggin polyanions

A new polyoxometalate-templated manganese-Schiff-base compound 1, {[Mn(L)₂]₂[PMo₁₂O₄₀][Cl] · DMF · 2CH₃CN · CH₃OH} _n (where L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene, DMF is N,N-dimethylformamide) has been synthesized by introducing the Metal-Schiff-base into polyoxometalates(POMs) at room temperature, and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The result of the single crystal X-ray diffraction suggested that the compound has the packing of the Mn(II)-Schiff-base cation layer and Keggin anion layer.     

Synthesis, Crystal Structure of Co(Ⅱ)(6-methoxybenzothiazole-2-carboxylate)_2(DMF)_2 and Its Application to Carbonylation of Benzyl Chloride

A new complex, Co(MBTC)₂(DMF)₂ (MBTC=6‐methoxybenzothiazole‐2‐carboxylate, DMF=N,N‐dime‐ thylformamide), was synthesized in DMF solution and characterized by single crystal X‐ray diffraction analysis. Using the cobalt complex as catalyst, phenylacetic acid was prepared by the carbonylation of benzyl chloride with carbon monoxide (0.1 MPa). The effects of solvents, phase transfer catalysts and temperature on the reactions were investigated. The yield of phenylacetic acid was higher than 90% in optimized condition.     

基于2,5-噻吩二甲酸的钙(Ⅱ)和钡(Ⅱ)配位聚合物的合成、晶体结构及性质

在溶剂热条件下,合成了2个碱土金属配位聚合物[Ca (tdc)(DMF)₂]_n(1)和[Ba (tdc)]_n(2)(H₂tdc=2,5-噻吩二甲酸),分别用元素分析、红外光谱、X射线单晶衍射、粉末衍射、热重分析和荧光光谱对它们进行了表征。结构分析表明,配合物1具有4,4连接的二维层状结构,拓扑符号为(4⁴·6²),而配合物2呈现三维网络结构。固体荧光测试表明配合物1比配合物2具有更显著的荧光性能。