A novel anionic metal–organic framework, JUC-138, constructed by In(III) and a pyrene-based linker, H8TIAPy (H8TIAPy = 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene), has been synthesized by solvothermal reaction successfully. In JUC-138, only four carbonyl groups in each ligand connect to In3+ ions, while the others remain uncoordinated. However, each In3+ connects to four carbonyl groups in a bidentate chelate style, resulting in the formation of 2D square sheets in JUC-138. The 2D sheets interact with adjacent layers through the O–H···O hydrogen bonds between the uncoordinated carboxyl groups, thus generating the whole 3D supramolecular structure of JUC-138. UV–vis tests show the energy gap Eg of JUC-138 is 3.34 eV, indicating the semiconductor nature of JUC-138. In addition, JUC-138 shows good photocatalytic activity in Azure B (AB) decolorization and could decompose 90% AB within 4 h. This photocatalytic property makes JUC-138 promising in environment governance.

•Porous aromatic framework-45 (PAF-45) was used for phenol removal firstly.•An improved method to prepare PAF-45 decreases synthesis time to one-tenth.•PAF-45 possesses good performance and great potential for industrial application.Download high-res image (399KB)Download full-size image

•HF adsorption capacities of four MOFs under unique conditions were studied.•MOFs have higher HF uptakes than commercial Al2O3 and 13X zeolite.•The HF adsorption of MIL-101(Cr) can be regenerated up to 90%.To avoid the health threat and environmental pollution as well as to preserve the life of industrial equipment, it is very important and necessary to find an efficient method for detecting and eliminating HF gas. In the present work, four MOFs including Cu-BTC, ZIF-8, MIL-53(Al) and MIL-101(Cr) with various surface area, functionalities, and pore sizes were selected for their HF adsorption capacities studied under unique conditions. As comparison, commercial Al2O3 powder and 13X zeolite were also investigated under the same conditions. It is resulted that the MOFs have higher HF uptakes than commercial Al2O3 and 13X zeolite. MIL-53(Al) have a highest HF capacity, and the HF adsorption of MIL-101(Cr) can be regenerated up to 90%. To the best of our knowledge, this is the first work of studying the HF adsorption behaviors of MOFs, which provides a new perspective of MOFs in a new field of practical purify application.Download high-res image (234KB)Download full-size image

A highly robust MOF based on a 12-carboxyl dendritic aromatic ligand and two Cd clusters is successfully synthesized. This activated MOF exhibits high heat of absorption of CO2 and highly selective adsorption of CO2 over CH4. Especially, a new type of topology (hhm-a) is presented.

Four new metal–organic frameworks (MOFs), namely, [Cu(PDIA)(DMA)]n (JUC-126), [Mn4(PDIA)4(DMF)6]n·nDMF·2nH2O (JUC-127), [Zn23(PDIA)18(μ4-O)2(μ3-OH)6DMA6]n·10nDMA·6nH2O (JUC-128), [Co3(PDIA)2(HCOO)(μ3-OH)(H2O)(DMA)2]n·nDMA·nH2O (JUC-129) (JUC = Jilin University, China), based on a new rigid ligand 5-(phenyldiazenyl)isophthalic acid (H2PDIA) with azobenzene were synthesized under solvothermal conditions. The ligand is connected to different metals to form bi-, tetra-, penta- and hexa-nuclear cores with distinctive coordination modes to generate different structures. Moreover, π–π stacking interactions between arene cores of the ligands also exist to affect the structural assembly process. JUC-126 displays a three-dimensional (3D) NbO topology with the point symbol (64·82) based on Cu2(COO)4 as secondary building units (SBUs), JUC-127 shows a two-dimensional (2D) sql topology with the point symbol (44·62) based on Mn2(COO)4 as SBUs, JUC-128 has a new 3D topology with the point symbol (33·46·56)2(36·48·510·64)3 based on Zn4O(COO)6 and Zn5(μ3-OH)2(COO)8 as SBUs and JUC-129 exhibits a 2D sql topology with the point symbol (44·62) based on Co6(μ3-OH)2(COO)10 as SBUs. In addition, JUC-126, JUC-128 and JUC-129 are achiral frameworks; however, JUC-127 shows a chiral framework from an achiral ligand. Furthermore, the luminescent property of JUC-128 and the magnetic properties of JUC-127 and JUC-129 have been studied and discussed.

We first designed and synthesized a new semirigid tripodal ligand with tetrazole groups, 1,3,5-tri(4-(2H-tetrazol-5-yl)phenoxy)benzene (H3TTPB). Two isostructural microporous metal–organic frameworks (MOFs), namely [Cu3(TTPB)2(H2O)6]·5DMF (JUC-130) and [Cd3(TTPB)2(H2O)6]·6DMF (JUC-131) (JUC = Jilin University, China), were successfully synthesized under solvothermal reactions based on this ligand, which both possess two-dimensional (2D) frameworks based on similar trinuclear metal centers as secondary building units (SBUs). H3TTPB was designed as the organic building block, not only because it is suitable to construct functionalized microporous frameworks with numerous nitrogen atoms but also by reason for its blue luminescent emission. Gas sorption measurements indicated that they are both microporous frameworks. JUC-130 showed high stability in water and selective sorption capabilities for alcohol and water vapors, which may be further used for the separation of alcohol–water mixtures. In addition, JUC-131 exhibited interesting and important fluorescent properties, which can be used as one of the few known MOFs useful for the detection of nitroaromatics via “supramolecular wire effect”.

•Two Cd MOFs have been prepared by solvent-induced strategy.•JUC-133 displays a new topology.•JUC-134 is a rutile (rtl) topology.Two cadmium-based metal–organic frameworks (MOFs), namely [Cd5(BTC)4(DMAc)2(H2O)2DMF]·2[H2N(CH3)2]·4DMAc (JUC-133) and [Cd3(BTC)2(DMSO)4] (JUC-134) (JUC = Jilin University, China), based on 1, 3, 5-benzenetricarboxylic acid ligand (H3BTC) were synthesized by solvent-induced strategy under solvothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, FT-IR spectroscopy, luminescent spectroscopy, TGA analysis, and powder X-ray diffraction. The ligand is connected to cadmium metals to form different cores with distinctive coordination modes to generate different structures. JUC-133 displays a new three-dimensional (3D) topology with the point symbol (4·62)4(4·82)4(42·65·83)4(86) based on Cd2(COO)5 and Cd2(COO)4 as secondary building units (SBUs), which is unknown in previously reported MOFs. JUC-134 can be symbolized as a rutile (rtl) topology with the point symbol (4·62)2(42·610·83) based on Cd3(COO)6 as SBUs. Furthermore, the luminescent of the ligand H3BTC and compounds were measured at room temperature. It is worth noting that the solvent could play an important role in the structural assembly process.Two cadmium-based metal–organic frameworks (MOFs), namely JUC-133 and JUC-134, based on 1, 3, 5-benzenetricarboxylic acid ligand (H3BTC) were synthesized by solvent-induced strategy under solvothermal conditions. JUC-133 displays a new 3D topology based on Cd2(COO)5 and Cd2(COO)4 as SBUs. In addition, JUC-134 can be symbolized as a rutile topology based on Cd3(COO)6 as SBUs.

•Two porous frameworks were obtained via the “pillaring” strategy.•The pillared frameworks were based on zinc and cadmic (6,3)-layers.•Zn and Cd lead to bilayers and 3-D open framework with hms topology, respectively.The (6,3)-layers of transition metals and 3,5-pyridinecarboxylate (3,5-PDC) containing terminal coordinated molecules offer a great potential for obtained porous frameworks via the “pillaring” approach. In this work, we have successfully obtained two porous frameworks based on the zinc and cadmic (6,3)-layers (compounds 1 and 2, respectively) pillared by 4,4′-pyridine (bipy). Interestingly, different metal centers of Zn(II) and Cd(II) in the (6,3)-layers lead to the pillared frameworks into bilayers with {63}{66} topology (compound 3) and 3-D open framework with {63}{69·8} hms topology (compound 4), respectively. It is believed that this work deserves further focus to enrich the design strategy of novel porous crystalline metal-organic frameworks (MOFs).The (6,3)-layers of transition metals and 3,5-pyridinecarboxylate (3,5-PDC) containing terminal coordinated molecules offer a great potential for obtained porous frameworks via the “pillaring” approach. In this work, we have successfully obtained two porous frameworks based on the zinc and cadmic (6,3)-layers pillared by 4,4′-pyridine (bipy). Interestingly, different metal centers of Zn(II) and Cd(II) in the (6,3)-layers lead to the pillared frameworks into bilayers with {63}{66} topology and 3-D open framework with {63}{69·8} hms topology. It is believed that this work deserves further focus to enrich the design strategy of novel porous crystalline metal-organic frameworks.

Two 2D multifunctional microporous metal–organic frameworks, [Cd3(L)2(H2O)6]·1.5H2O·2EtOH·DMF (1, H3L = 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine) and [Zn3(L)2(H2O)2]·3H2O·TEA·2DMF (2), with single- and double-(6,3)-layer structures, respectively, have been synthesized by the reaction of Cd(Zn) nitrate with H3L in a mixed solvent of DMF, ethanol, and H2O. TGA and PXRD analysis showed that compounds 1 and 2 were thermally stable up to 250 °C. Gas sorption measurement indicates that compounds 1 and 2 exhibited selective sorption capabilities for CO2 over CH4 and N2 and could adsorb considerable amounts of H2 at low temperature. These two compounds also showed high sorption capabilities for water, methanol, and ethanol vapors. The highest adsorption amounts of compounds 1 and 2 are 168.8 and 257.3 cc/g for H2O, 175.1 and 140.8 cc/g for methanol, and 91.7 and 76.2 cc/g for ethanol, respectively. Furthermore, the maximum luminescence emission peaks of compounds 1 and 2 exhibit blue shifts of 138 and 132 nm, respectively, compared to the free ligand.

•We obtained three new MOFs based on pyridine-3,5-dicarboxylic acid.•JUC-58 is 3-d homochiral MOFs, while JUC-59-M (M = Co, Ni) has a lig-b net.•Glycol could play an important role in the formation of the MOFs.Three new metal–organic frameworks Mn(3,5-PDC)(H2O)•(glycol) (JUC-58), M(3,5-PDC)(H2O)(glycol)•(H2O) (JUC-59-M, M = Co, Ni), have been synthesized by the assembly of tri-connected ligand pyridine-3,5-dicarboxylic acid (3,5-PDC) and different metals under the solvothermal condition in DMF and glycol. JUC-58 is an unusual example of 3-D chiral MOF with helical channels, while JUC-59-Co and JUC-59-Ni are isostructural and have non-centrosymmetric structures with a very rare 3-connected non-interpenetrated lig-b net. It is worth noting that glycol could play an important role in the formation and stabilization of these networks.Graphical abstractJUC-58 and JUC-59-Co, Ni were synthesized by pyridine-3,5-dicarboxylic acid and different metals under solvothermal condition in DMF and glycol. JUC-58 is homochiral, while JUC-59-Co, Ni have a lig-b net. It is worth noting that glycol could play an important role in the formation and stabilization of the MOFs.

We report the facile synthesis of ZIF-8 nanocrystals in an urea–choline chloride eutectic mixture. It was found that the concentration of reactant plays an important role in the crystal size. The experimental results also revealed that the addition amount of water and ethanol could affect the size and the dispersion of the as-synthesized ZIF-8 nanocrystals.

Two novel metal–organic frameworks (MOFs) assembled from H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O} 1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2′,6,6′-tetracarboxylic acid, DMF = N,N-dimethylformamide) have been obtained under hydrothermal conditions, and structurally characterized by single-crystal X-ray diffraction. The results reveal that compounds 1 and 2 are isostructural except the different metal centers, exhibiting a 2D layer structure with 4–4 net. 1 and 2 are also characterized by elemental analysis, IR spectra, TGA analysis and PXRD. The luminescent properties of 1 and 2 in solid state are discussed.Two novel 2D metal–organic frameworks (MOFs) based on H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O}1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2,6′,6′-tetracarboxylic acid, DMF = N,N′-dimethylformamide) have been obtained under hydrothermal conditions, and well characterized by single-crystal X-ray diffraction,elemental analysis, IR spectra, TGA analysis, PXRD and luminescent spectra. The results reveal that these two compounds are isostructural except the different metal centres, exhibiting a 2D layer structure with 4-4 net.Highlights► We obtained two novel MOFs from a kind of tetracarboxylic acid ligand. ► These two compounds are isostructural exhibiting layers with 4-4 net. ► Luminescence of compounds in solid state are blue-shifted from free ligand.

A highly robust MOF based on a 12-carboxyl dendritic aromatic ligand and two Cd clusters is successfully synthesized. This activated MOF exhibits high heat of absorption of CO2 and highly selective adsorption of CO2 over CH4. Especially, a new type of topology (hhm-a) is presented.