一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5，5''-di (1H-1，2，4-triazol-1-yl)-(1，1''-biphenyl)-2，2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应，制备了一个结构新颖的金属有机骨架{[Co (DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔，还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50∶50)混合气中选择性吸附C₂H₂，还可以从CO₂/N₂(体积比15∶85)和CO₂/CH₄(体积比50∶50)混合气中选择性捕获CO₂；固定床突破实验进一步证实了其高效的气体分离能力。     

一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5，5''-di (1H-1，2，4-triazol-1-yl)-(1，1''-biphenyl)-2，2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应，制备了一个结构新颖的金属有机骨架{[Co (DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔，还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50∶50)混合气中选择性吸附C₂H₂，还可以从CO₂/N₂(体积比15∶85)和CO₂/CH₄(体积比50∶50)混合气中选择性捕获CO₂；固定床突破实验进一步证实了其高效的气体分离能力。     

基于半刚性配体的柔性超微孔金属有机骨架的合成及其尺度选择性二氧化碳捕获

基于半刚性的配体3'',5''-di(1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-3,5-dicarboxylicacid(H₂DTBDA)和硝酸钴制备了一个柔性超微孔的金属有机骨架{[Co(DTBDA)]·4H₂O}_n(FJI-H35),并对该材料的结构进行了系统的表征。FJI-H35活化以后可以发生自适应的结构转变,使得孔径从0.43nm收缩到0.37nm。气体吸附测试表明FJI-H35可以从氮气和甲烷中选择性捕获二氧化碳,具有很高的吸附选择性和相对低的吸附焓。突破实验进一步证实FJI-H35可以从二氧化碳/氮气(15∶85,V/V)和二氧化碳/甲烷(50∶50,V/V)混合气中高效选择性捕获二氧化碳。     

基于半刚性配体的柔性超微孔金属有机骨架的合成及其尺度选择性二氧化碳捕获

基于半刚性的配体3'',5''-di (1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-3,5-dicarboxylic acid (H₂DTBDA)和硝酸钴制备了一个柔性超微孔的金属有机骨架{[Co (DTBDA)]·4H₂O}_n(FJI-H35),并对该材料的结构进行了系统的表征。FJI-H35活化以后可以发生自适应的结构转变,使得孔径从0.43 nm收缩到0.37 nm。气体吸附测试表明FJI-H35可以从氮气和甲烷中选择性捕获二氧化碳,具有很高的吸附选择性和相对低的吸附焓。突破实验进一步证实FJI-H35可以从二氧化碳/氮气(15∶85,V/V)和二氧化碳/甲烷(50∶50,V/V)混合气中高效选择性捕获二氧化碳。     

由酰胺四酸配体构建的一个微孔三维金属有机骨架化合物及其高效可逆碘吸附性能

合成并表征了一个由酰胺键修饰并带有π-电子内壁的微孔三维金属有机骨架化合物[Cu₅(L)₂(H₂O)₅] (1) (H₄L=5,5'-((1H-pyrazole-3,5-dicarbonyl)bis(azanediyl))diisophthalic))。拓扑分析表明1为(3,3,4,4,6)-连接类型的网络结构,同时通过氮气和二氧化碳气体吸附验证了其孔道性质。同时1可以作为碘分子吸附的良好主体(1.94 mmol·g^-1,室温),并在碘分子的可逆吸附中具有出色的表现。     

以5-(3-吡啶基)-1H-吡唑-3-羧酸为配体的钴共晶配合物的合成、晶体结构及电化学性质

采用溶剂热法合成了一种新型的钴(Ⅱ)基配合物,即{[Co(Hppc)₂][Co₂(4,4''-bipy)(H₂O)₄](SO₄)₂·2H₂O}_n (1),其中H₂ppc=5-(3-吡啶基)-1H-吡唑-3-羧酸,4,4''-bipy=4,4''-联吡啶。配体H₂ppc是由吡啶环、吡唑环和羧基共同组成,同时兼具了刚性和柔性。通过单晶X射线衍射对配合物1进行了结构测定。结果显示所合成的配合物1结晶在单斜晶系C2/c空间群,包括2个晶体学独立部分：二维层状[Co(Hppc)₂]和一维链状[Co₂(4,4''-bipy)(H₂O)₄]^2-,并形成具有{4⁴·6²}{4}₂拓扑网络结构的共晶化合物。此外,配合物1呈现出良好的电化学发光(ECL)性能以及良好的超级电容器性能。     

基于1, 1′-苯乙炔-3, 3′, 5, 5′-四羧酸微孔铜配位聚合物的合成和气体吸附性质

本文报道了配合物[Cu₂(EBTC)(H₂O)₂]·8H₂O·DMF·DMSO(1, EBTC=1, 1′-乙炔基苯-3, 3′, 5, 5′-四羧酸根;DMF=N, N-二甲基甲酰胺;DMSO=二甲基亚砜)的合成、晶体结构和吸附性质。1拥有内径为0.85 nm和0.85 nm×2.15 nm的两种孔洞, 分别被6个和12个四羧酸根桥联的[Cu₂(CO₂)₄]螺旋桨式结构围绕, 并被EBTC连接成三维超分子结构, 该结构拥有可容纳溶剂分子的一维孔道。1为(3, 4)-连接的fof(sqc1575)拓扑结构, 具有非常大的孔体积, 其值高达单位晶胞体积的72.8%。去除溶剂分子后的1a表现出永久孔性, 其Langmuir表面积为2844 m²·g^-1, BET 表面积为1 852 m²·g^-1。它对H₂、CO₂、CH₄和C²H₂具有可观的气体吸附量和相对较高的吸附焓。特别是, 在迄今所有已报道的孔性金属-有机材料中, 1a在273 K、1.0×10⁵ Pa下, 表现出最高的乙炔吸附量(252 cm³·g^-1)和很高的吸附焓(吸附量为1 mmol·g^-1时的吸附焓为34.5 kJ·mol^-1)。     

两个配位竞争策略制备的镁基金属有机骨架及其选择性CO2捕集

利用配位竞争策略制备了2个镁基金属有机骨架(MOFs)。在酸性条件下,镁离子与N,N-二甲基甲酰胺(DMF)热分解产生的甲酸原位反应得到三维甲酸镁 MOF：[Mg₃(HCO₂)₆]·DMF (1)。在相同条件下,当加入竞争配体 1,1′∶3′,1″-三联苯-3,3″,5,5″-四甲酸(H₄L)后,甲酸不再参与配位,得到新的三维镁基MOF：[Mg₂(L)(H₂O)₃]·2 H₂O·2CH₃CN·DMF (2)。单晶X射线分析表明,MOF 1具有[Mg₄@Mg2]四面体建筑块,它们形成dia拓扑网络并有一个孔径为0.44 nm的一维孔道。而MOF 2具有独特的[Mg₂]双核簇,与4-连接配体L^4-配位后,形成sra拓扑网络且沿a轴方向存在一个哑铃型孔道,长度为1.42 nm。气体吸附研究发现1具有微孔结构,其表面积为342 m²·g^-1,但2不能保持原有多孔特征。此外,1具有良好的水稳定性且在低压下展现快速吸收的Ⅰ型 CO₂吸附等温线,在 298 K和 2 000 kPa下吸附量达到样品重量的 14.5%。理想吸附溶液理论和吸附热计算表明 1具有良好的选择性CO₂/CH₄捕获能力。     

环己烷甲酸根桥联的二维锰配合物的合成与表征

Complex [Mn₂(C₆H₁₁CO₂)₃(4,4′-bipy)₂(H₂O)₂]ClO₄ (C₆H₁₁CO₂H=cyclohexanecarboxylic acid) was synthesized by reaction of Mn(ClO₄)₂·6H₂O, C₆H₁₁CO₂Na and 4,4′-bipy in methanol. The title complex crystallizes in triclinic space group P1, with a=1.008 8(2) nm, b=1.086 3(1) nm, c=1.164 9(3) nm, α=63.016(3)°, β=81.998(4)°, γ=88.604(1)°, V=1.125 4(4) nm³, Z=1. There are two types of Mn atoms in the structure with each in octahedral geometry. Mn1 and Mn2 are bridged by cyclohexanecarboxylate ligands into a chain and the chains are further linked together by 4,4′-bipy into a 2D plane. CCDC: 692247.     

基于醚氧桥联四羧酸配体构筑的三个钴(Ⅱ)、铜(Ⅱ)和镉(Ⅱ)配位聚合物的合成、结构和在Knoevenagel缩合反应中的催化性质

采用水热方法,选用醚氧桥联四羧酸配体H4dia与菲咯啉(phen)、2,2''-联吡啶(bipy)或双(4-吡啶基)胺(bpa)分别与CoCl₂·6H₂O、CuCl₂·2H₂O和CdCl₂·4H₂O在160℃下反应,得到了一个一维链结构[Co₂(μ₄-dia)(phen)₂(H₂O)₂]_n (1)和2个三维网络结构的配位聚合物[Cu₂(μ₆-dia)(bipy)₂]_n (2)和{[Cd₂(μ₅-dia)(μ-bpa)2(H₂O)]·H₂O}_n (3),并对其结构和催化性质进行了研究。研究表明,在50℃下配合物2在Knoevenagel缩合反应中显示出很好的催化活性。     

通过有机配体中四嗪基团的原位水解提高金属有机框架的CO2吸附性能

在保持原有"层-柱"MOF[Zn₄（bpta）₂（dipytz）₂（H₂O）₂]·4DMF·H₂O （1）（H₄bpta=2,2'',6,6''-联苯四羧酸,dipytz=3,6-二（4-吡啶基）-1,2,4,5-四嗪）主体结构不变的情况下,通过dipytz配体中四嗪环的原位水解反应将极性的二芳酰基联氨基团引入框架,成功构筑出配合物[Zn₄（bpta）₂（dipytz_hydr）₂（H₂O）₂]·solvent （2）（dipytz_hydr=1,2-二异烟酰基肼）。对配合物2的系统表征和气体吸附性质研究结果证实了功能化目标的实现：配合物2相比于配合物1展现出更高的二氧化碳吸附热（由28.8 kJ·mol^-1升高至30.3 kJ·mol^-1）和CO₂/CH₄吸附选择性。以上结果表明基于配体中四嗪基团的原位水解后修饰能够有效提高相关MOFs材料的CO₂吸附性能。     

Nanocage containing metal-organic framework constructed from a newly designed low symmetry tetra-pyrazole ligand

1368-Tetra(1H-pyrazol-4-yl)-9H-carbazole (H₄CTP), a tetra-pyrazole ligand with C_s symmetry, has been synthesized based on a carbazole core. A solvothermal reaction of this ligand with NiCl₂·6H₂O gave a three-dimensional (3-D) metal-organic framework (MOF), [Ni(H₄CTP)Cl₂]·nS (BUT-41), which crystallized in the cubic space group Pm-3 in spite of H₄CPT with a central carbazole core and four peripheral pyrazole rings has low symmetry. The framework of BUT-41 can be regarded as a four-connected 3-D net with the rhr topology when both the organic ligand and the metal center are considered as four-connected nodes. Nanocages with internal diameter of 2 nm are present in the framework of BUT-41, which are formed by interconnecting 12 H₄CTP ligands and 20 Ni(II) ions. Each nanocage connects with six adjacent cages through sharing hexagonal windows with diameter over 7 Å, resulting in 3-D intersecting channels of the MOF. Although the tetra-pyrazole ligand is not deprotonated after coordination with the metal ions, powder X-ray diffraction and N₂ adsorption experiments reveal that the framework of BUT-41 is rigid and permanently porous with the Brunauer-Emmett-Teller surface area up to 1551 m² g^?1. Furthermore, gas adsorption experiments show that this MOF selectively adsorbs CO₂ over N₂ and CH₄.     

基于1,1’-二苯乙炔-3,3’,5,5’-四羧酸微孔铜配位聚合物的合成和气体吸附性质

本文报道了配合物[Cu2(EBTC)(H2O)2]·8H2O·DMF.DMSO(1,EBTC=1,1′-二苯乙炔-3,3′,5,5′-四羧酸根;DMF=N,N-二甲基甲酰胺;DMSO=二甲基亚砜)的合成、晶体结构和吸附性质。1拥有内径为0.85 nm和0.85 nm×2.15 nm的两种孔洞,分别被6个和12个四羧酸根桥联的[Cu2(CO2)4]螺旋桨式结构围绕,并被EBTC连接成三维超分子结构,该结构拥有可容纳溶剂分子的一维孔道。1为(3,4)-连接的fof(sqc1575)拓扑结构,具有非常大的孔体积,其值高达单位晶胞体积的72.8%。去除溶剂分子后的1a表现出永久孔性,其Langmuir表面积为2844 m2·g-1,BET表面积为1 852 m2·g-1。它对H2、CO2、CH4和C2H2具有可观的气体吸附量和相对较高的吸附焓。特别是,在迄今所有已报道的孔性金属-有机材料中,1a在273 K、1.0×105Pa下,表现出最高的乙炔吸附量(252 cm3·g-1)和很高的吸附焓(吸附量为1 mmol·g-1时的吸附焓为34.5 kJ·mol-1)。     

Synthesis,characterization, and urease inhibitory activity of two copper(II) complexes of cyclohexanecarboxylate

The crystal structures of two copper(II) complexes of the cyclohexanecarboxylate ligand, namely [Cu(C₆H₁₁CO₂)₂(H₂O)₂]·H₂O (1) and [Cu(dpyam)₂(C₆H₁₁CO₂)](NO₃)·H₂O (2) (C₆H₁₁CO₂H = cyclohexanecarboxylic acid; dpyam = di-2-pyridylamine), have been determined by single-crystal X-ray analysis. Complex 1 contains the square-planar trans-CuO₄ chromophore, while 2 shows the square pyramidal cis-distorted octahedral CuN₄OO′ chromophore. Both complexes were found to show strong inhibitory activity against jack bean urease (IC₅₀ = 1.75 and 8.57 μM for 1 and 2, respectively), when compared with acetohydroxamic acid (IC₅₀ = 63.12 μM).     

Optimizing Acetylene Sorption through Induced-fit Transformations in a Chemically Stable Microporous Framework

Developing practical storage technologies for acetylene (C₂H₂) is important but challenging because C₂H₂ is useful but explosive. Here, a novel metal–organic framework (MOF) ( FJI-H36 ) with adaptive channels was prepared. It can effectively capture C₂H₂ (159.9 cm³ cm⁻³) at 1 atm and 298 K, possessing a record-high storage density (561 g L⁻¹) but a very low adsorption enthalpy (28 kJ mol⁻¹) among all the reported MOFs. Structural analyses show that such excellent adsorption performance comes from the synergism of active sites, flexible framework, and matched pores; where the adsorbed-C₂H₂ can drive FJI-H36 to undergo induced-fit transformations step by step, including deformation/reconstruction of channels, contraction of pores, and transformation of active sites, finally leading to dense packing of C₂H₂. Moreover, FJI-H36 has excellent chemical stability and recyclability, and can be prepared on a large scale, enabling it as a practical adsorbent for C₂H₂. This will provide a useful strategy for developing practical and efficient adsorbents for C₂H₂ storage.     

Syntheses of(C_8H_8)Ln(C_9H_7)·(THF)_2(Ln=Pr,Nd)and crystal structure of(C_8H_8)Pr(C_9H_7)·(THF)_2

This paper reports two lanthanide complexes of formula (C_9H_7)Ln(C_8H_8)·(THF)_2 whereLn is Pr or Nd,C_9H_7 is indenyl,and C_8H_8 is cyclooctatetraene (COT).The complexes were preparedby the reaction of LnCl_3 with K(C_9H_7) and K_2(C_8H_8) in THF.(C_9H_7)Pr(C_8H_8)·(THF)_2 crystallizes inTHF at - 15℃ in the monoclinic space group P2_1:with unit cell dimensions a=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)~3,Dc=1.52g/cm~3 and Z=2.The final R valueis 0.033,R_w value is 0.030,respectively.In (C_9H_7)Pr(C_8H_8)·(THF)_2 a five-membered ring centroid ofC_9H_7,the C_8H_8 ring centroid and the two oxygen atoms from the two THF molecules form a distortedtetrahedral geometry around the metal.     

Preparation,Structure and Thermal Decomposition of Cu(II) Complexes with 2-Chloro- and 2,3-Dichlorobenzoic Acids and Imidazole

The reaction products of Cu(II) 2-chlorobenzoate and imidazole (1), and of Cu(II) 2,3-dichlorobenzoate and imidazole (2) formulated as CuL'₂·3imd and CuL"·3imd (L' = C₇H₄ClO₂, L" = C₇H₄Cl₂O₂ ^?, imd = imidazole), were prepared and characterized by means of structural and spectroscopic measurements and thermochemical properties. The blue (1) and green (2) compounds crystallize in the monoclinic system with space group C2/c, cell parameters a = 20.753(4), b = 8.414(2), c = 14.429(3) Å, β = 90.15(3)°, V = 2519.5(9) &Aringsup3;, Z = 4 for (1) and a = 21.335(4), b = 8.417(2), c = 15.030(3) Å, β = 94.11(3)°, V = 2692.1(10) &Aringsup3;, Z = 4 for (2). The complexes decompose at 483 K.     

Construction of a Stable Crystalline Polyimide Porous Organic Framework for C2H2/C2H4 and CO2/N2 Separation

Utilization of porous materials for gas capture and separation is a hot research topic. Removal of acetylene (C₂H₂) from ethylene (C₂H₄) is important in the oil refining and petrochemical industries, since C₂H₂ impurities deactivate the catalysts and terminate the polymerization of C₂H₄. Carbon dioxide (CO₂) emission from power plants contributes to global climate change and threatens the survival of life on this planet. Herein, 2D crystalline polyimide porous organic framework PAF-120, which was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular 1,3,5-tris(4-aminophenyl)benzene, showed significant thermal and chemical stability. Low-pressure gas adsorption isotherms revealed that PAF-120 exhibits good selective adsorption of C₂H₂ over C₂H₄ and CO₂ over N₂. At 298 K and 1 bar, its C₂H₂ and CO₂ selectivities were predicted to be 4.1 and 68.7, respectively. More importantly, PAF-120 exhibits the highest selectivity for C₂H₂/C₂H₄ separation among porous organic frameworks. Thus PAF-120 could be a suitable candidate for selective separation of C₂H₂ over C₂H₄ and CO₂ over N₂.     

Synthesis and physicochemical characterization of nanocrystalline chitosan-containing calcium carbonate apatites

The CaCl₂-(NH₄)₂HPO₄-NH₄HCO₃-(C₆H₁₁NO₄) _n -H₂O system at 25°C has been investigated by the solubility (Tananaev’s residual concentration) method and pH measurements. Coprecipitation conditions have been determined for nanocrystalline type A and B calcium carbonate apatites. Type A: Ca₁₀(PO₄)₆(CO₃) _x (OH)_{2 − 2x} · yC₆H₁₁NO₄ · zH₂O (x = 0.2, 0.5, 1.0; y = 0.1, 0.3, 0.5; z = 5.3−6.7); type B: Ca₁₀[(PO₄)_5.7(CO₃)_0.45]CO₃ · 0.3C₆H₁₁NO₄ · 9H₂O, and Ca₁₀[(PO₄)_5.55(CO₃)_0.675]CO₃ · 0.3C₆H₁₁NO₄ · 9.2H₂O. The solid phases have been characterized by chemical analysis, X-ray diffraction, thermogravimetric analysis, and IR spectroscopy.     

Rare Earth Chalcogels NaLnSnS4 (Ln = Y,Gd, Tb) for Selective Adsorption of Volatile Hydrocarbons and Gases

The synthesis and characterization of the rare earth chalcogenide aerogels NaYSnS₄, NaGdSnS₄, and NaTbSnS₄ is reported. Rare earth metal ions like Y³⁺, Gd³⁺, and Tb³⁺ react with the chalcogenide clusters [SnS₄]^4– in aqueous formamide solution forming extended polymeric networks by gelation. Aerogels obtained after supercritical drying have BET surface areas of 649 m² · g^–1 (NaYSnS₄), 479 m² · g^–1 (NaGdSnS₄), and 354 m² · g^–1 (NaTbSnS₄). Electron microscopy and physisorption studies reveal that the new materials have pores in the macro (above 50 nm) and meso (2–50 nm) regions. These aerogels show higher adsorption of toluene vapor over cyclohexane vapor and CO₂ over CH₄ or H₂. The notable adsorption capacity for toluene (NaYSnS₄: 1108 mg · g^–1; NaGdSnS₄: 921 mg · g^–1; and NaTbSnS4: 645 mg · g^–1) and high selectivity for gases (CO₂/H₂: 172 and CO₂/CH₄: 50 for NaYSnS₄, CO₂/H₂: 155 and CO₂/CH₄: 37 for NaGdSnS₄, and CO₂/H₂: 75 and CO₂/CH₄: 28 for NaTbSnS₄) indicate potential future use of chalcogels in adsorption‐based gas or hydrocarbon separation processes.