Two series of chemically and thermally stable rare-earth MOFs were constructed using trinuclear [M3(μ3-OH)(COO)6] SBUs and linear dicarboxylate linkers, which feature three-dimensional 12-connected frameworks with an hcp topology. These materials contain a large density of Lewis acidic sites, leading to high catalytic activity towards the cycloaddition of CO2 and epoxides under mild conditions.

A microporous hexanuclear europium cluster based MOF, (DMA)2[Eu6(μ3-OH)8(BPDC)6(H2O)6]n·(solv)x (DMA = dimethylamine cation and H2BPDC = [1,1′-biphenyl]-4,4′-dicarboxylic acid), can be applied as a highly selective and sensitive bifunctional luminescence sensor to detect nitrobenzene and 4-aminophenol through an energy competition mechanism. More interestingly, this MOF can detect nitrobenzene and 4-aminophenol with low detection limits of 5–70 ppm and 5–110 ppm, respectively.

MOF-templated nitrogen-doped porous carbon materials (NPCs) have been prepared by employing the previously reported MOF, [(CH3)2NH2]6[Ni(H2O)6]3{Ni6(η6-TATAT)4(H2O)12}, as a precursor, which can act as efficient electrocatalysts for oxygen reduction reactions (ORRs). The carbonized MOF acts as the carbon source, and urea is employed as an additional nitrogen source. The urea modified carbon materials, carbonized at 800 °C, 900 °C and 1000 °C under Ar atmosphere, all show electrocatalytic activity for ORRs; the material carbonized at 900 °C exhibits a more appropriate nitrogen content, robust pore structure and an excellent degree of graphitization. In alkaline media, NPC-900 exhibits superior catalytic activity (the onset and half-wave potentials are −0.06 V and −0.23 V vs. Ag/AgCl, respectively), excellent long-term durability and outstanding methanol tolerance compared with the commercial Pt/C catalyst.

•High performance electrochromic film is prepared using electrodeposition method.•Isopolyacid decatungstate is employed as the electrochromic material.•The transmittance could reduce from 98.0% down to 50.8% at the wavelength of 550 nm.•The composite film also exhibits high reversibility and durability.In this work, porous decatungstate-TiO2 composite thin film has been prepared by the electrodeposition method. The advantages of decatungstate as electrochromic material are discussed and the electrochromic performances of the composite film have also been systematically investigated. The transmittance decreased from 98.0% down to 50.8% at the wavelength of 550 nm under an applied potential of − 0.8 V. Good reversibility and reproducibility also can be observed in the composite electrochromic film. The porous structure of the composite film not only provides a large surface area for loading W10 polyanions but is also beneficial for the fast diffusion of H+, which results in high electrochromic performances.

An In-based metal–organic framework, with 1D nanotubular open channels, In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (1), has been synthesized via an in situ ligand reaction, in which 1,2,4-H3btc is partially transformed into the L ligand. Compound 1 exhibits exceptional thermal and chemical stability, especially in water or acidic media. The activated 1 presents highly selective sorption of carbon dioxide (CO2) over dinitrogen. Interestingly, diffuse-reflectance infrared Fourier transform spectroscopy with a carbon monoxide probe molecule demonstrates that both Lewis and Brønsted acid sites are involved in compound 1. As a result, as a heterogeneous Lewis and Brønsted acid bifunctional catalyst, 1 possesses excellent activity and recyclability for chemical fixation of CO2 coupling with epoxides into cyclic carbonates under mild conditions. In addition, the mechanism for the CO2 cycloaddition reaction has also been discussed.

Three isomorphous lanthanide–organic polyrotaxane frameworks [Ln(mtpc)1.5(DMA)(H2O)]·2H2O [Ln = Tb (1); Dy (2); Er (3)] were assembled and characterized. In 1, the mtpc ligand transfer absorbed energy to Tb3+ center to emit characteristic fluorescence. 1 can act as a fluorescent probe for selectively detecting nitrobenzene and iron(III) ions through luminescence quenching. Importantly, the detection limit of nitrobenzene is on the 15–150 ppm scale.

•Pd(II) complexes controlled by the aliphatic chain of benzenealkyl dicarboxylate ligand•The structures, cytotoxicity, apoptosis and molecular docking were investigated.•The good visualization images supported with the experimental results.•Structure–activity relationship between cytotoxicity and carbon chain lengthA new series of Pd(II) complexes derived from benzenealkyl dicarboxylate ligands, [Pd(Ln)(phen)] (phen = 2,9-dimethyl-1,10-phenanthroline, complex 1: L1 = phenylmalonate; complex 2: L2 = benzylmalonate; complex 3: L3 = (2-phenylethyl)malonate; complex 4: L4 = (3-phenylpropyl)malonate) have been synthesized under room temperature condition. These complexes contain a long dicarboxylate aliphatic chain. They were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction. The binding of complexes with fish sperm DNA (FS-DNA) was investigated by UV absorption and fluorescence spectra. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pBR322 plasmid DNA. The cytotoxic activity of the complexes was tested against two different cancer cell lines, HeLa and HL-60. Cytotoxic activity studies showed the four complexes exhibited significant cancer cell inhibitory rate. Further flow cytometry experiments showed that the cytotoxic Pd(II) complexes induced apoptosis of HL-60 tumor cell lines. The molecular dynamic simulations and docking methods were used to predict the DNA binding affinity of Pd(II) complexes by the resulting relative binding energy of complexes with DNA − 6.01, − 6.25, − 7.24 and − 7.59 kcal/mol, while with DNA-topoisomerase I (Topo I) − 7.98, − 9.25, − 10.2 and − 11.5 kcal/mol, respectively. The good visualization images supported with the experimental results of structure–activity relationship between cytotoxicity and carbon chain length.A new series of Pd(II) complexes were synthesized and characterized. The visualization images supported with the experimental results of structure–activity relationship between cytotoxicity and carbon chain length.

•A photoluminescent complex based on trinuclear Cd(II) clusters have been successfully synthesized.•This complex displays strong fluorescent emission both in the solid state and in methanol suspension at room-temperature.•This complex can selective sensing Zn2+ through luminescent emission enhancement among other metal ions.•This complex can selective sensing nitrobenzene through luminescent emission quenching among other nitroaromatics.Cd(II)-organic coordination polymer with the formula [Cd3(btdc)3(DMF)2(EtOH)2]·2EtOH·2H2O were solvothermally synthesized by treating Cd(II) nitrates with 2,2′-bithiophene-5,5′-dicarboxylic acid (H2btdc) and characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetric analyses, IR spectroscopy and X-ray powder diffraction. Single-crystal X-ray diffraction studies indicate that the Cd(II) complex exhibits a 3D supramolecular framework, in which trinuclear Cd(II) clusters are connected by btdc ligands to form a 2D (4, 4) layer. Furthermore, the 2D (4, 4) layers stacked via AA mode. This complex displays strong fluorescent emission both in the solid state and in methanol suspension at room temperature, which can act as the fluorescent probe for selectively detecting Zn2+ ions and nitrobenzene through luminescence enhancing and quenching, respectively.A 3D Cd(II)-organic coordination polymer composed of Cd(II) clusters and btdc ligands was constructed, in which trinuclear Cd(II) clusters are connected by btdc ligands to form a 2D (4, 4) layer. The adjacent 2D layers are stacked via AA mode to generate a 3D framework. The Cd(II) complex displays strong fluorescent emission both in the solid state and in methanol suspension at room temperature. In addition, the fluorescent of this complex can be enhanced by adding Zn2+ ions and quenched by adding nitrobenzene. Such phenomenon can be applied for Zn2+ ions or nitrobenzene selective sensing.

In this paper, we develop a facile and convenient two-step strategy for preparation of ZIF-8/ZnO/K6P2W18O62 (P2W18) ternary composite materials for the first time. ZIF-8/ZnO are fabricated by a “direct mixing” synthesis strategy and served as the substrate for subsequent P2W18 deposition. Then, ZIF-8/ZnO/P2W18 ternary composite was prepared in P2W18 aqueous solution through electrostatic interaction process. Further, the composites with different loading of P2W18 were achieved by reacting with different concentration of P2W18 aqueous solution. The as-prepared composite materials were characterized and confirmed by powder X-ray diffraction, TEM, EDS, ICP, FT-IR spectra, UV–Vis diffuse reflectance spectroscopy, and electrochemical test. It is noteworthy that the hybrid composites exhibit high efficient activities in the removal of cationic dyes, which could be ascribed to the high adsorption capacity derived from the strong electrostatic interaction between P2W18 and cationic dyes. Based on the investigation, the composites have potential application for waste water purification.

An InIII-based anionic framework (InIII-MOF) with 4-connected SrAl2 topology was constructed. The InIII-MOF with permanent porosity functions as a host for encapsulation of Ln3+ ions through ion-exchange processes. The photophysical properties of the as-prepared Ln3+@InIII-MOF were investigated and the results showed that the InIII-MOF could serve as an antenna to sensitize Ln3+ cations, especially suitable for Tb3+ and Eu3+ ions. The possible sensitization mechanism has been studied by surface photovoltage spectroscopy. Additionally, the InIII-MOF could also act as a host material when applied in the separation and purification of cationic dyes, which is highly based on the size and charge of organic dyes. Moreover, it can be used as a chromatographic column stationary phase to separate cationic dyes more efficiently and selectively. It is believed that the as-prepared InIII-MOF may have potential applications in optical materials and environmental fields.

Herein, two stable lead(II) molecular-bowl-based metal–organic frameworks and their micro- and nanosized forms with open metal sites were presented. These materials could act as Lewis acid catalysts to cyanosilylation reaction. Moreover, the catalytic performances are size-dependent, with the catalyst with nanosized form being 1 order of magnitude more efficient than those with micro- and millisized forms.

A luminescent metal–organic framework was assembled by using 3,3′-((6-hydroxy-1,3,5-triazine-2,4-diyl)bis(azanediyl))dibenzoic acid and Zn(II), which exhibits a 2D layer architecture, and the adjacent layers are further stacked via hydrogen-bonding and N···N van der Waals interactions to form a 3D supramolecular framework. This material can be used as fluorescent probe of K+ ion.

Three three-dimensional (3D) coordination polymers with the formulae [Cd(TPTC)0.5(H2O)2] ·DMA (1), [Co2(TPTC)(H2O)1.5(CH3OH)0.5] (2), and [Mn2(TPTC)(H2O)(DMA)]·DMA (3) (TPTC = [1,1′:4′,1′′-terphenyl]-2′,4,4′′,5′-tetracarboxylate acid) were solvothermally synthesized. They were characterized by thermogravimetric analyses, IR spectroscopy, X-ray powder diffraction, and single crystal X-ray diffraction. 1 features a 3D porous coordination polymer formed from Cd-carboxylate chains and the TPTC bridges. In 2 and 3, the uniform metal–carboxylate chains with triple bridges, (μ-EO-H2O)(μ-syn,syn-COO)2 and (μ-EO-H2O/DMA)(μ-syn,syn-COO)2 (EO = end-on), were extended by the TPTC arms. Complex 1 displayed strong fluorescent emission in the visible region. Interestingly, the emission intensities of 1 were increased upon the addition of Al3+ and quenched upon the addition of Fe3+, even in mixtures of ions. Thus, 1 can act as a useful material for sensing Fe3+ and Al3+ ions. The magnetic studies of 2 and 3 show that antiferromagnetic interactions between the Co(II) and Mn(II) centers exist.

•A new 3D coordination polymer has been constructed.•This complex displays strong fluorescent emissions at room temperature.•This complex can selectively sense Fe3 + ions through fluorescence quenching.A new 3D coordination polymer [NH2(CH3)2]2[Zn7L4(DMF)2(H2O)3]·19H2O (1) (L = 2,3′,5,5′-biphenyl tetracarboxylic acid) has been solvothermally synthesized and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that 1 exhibits 3D framework with a one-dimensional (1D) channel. The luminescence properties have been studied, and the results showed that 1 displays strong fluorescent emissions both in the solid state and in methanol suspension at room temperature. More interesting, the addition of Fe3 + causes the fluorescence intensity of 1 to be weakened, which implies that it may be used as luminescent probes of Fe3 +.

A new coordination polymer [Gd(Sfdb)(NO3)(DMF)2] · 2H2O (Sfdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction (CIF file CCDC no. 1023460). The X-ray diffraction analysis shows that I (C20H24N3O12SGd) crystallizes in the monoclinic crystal system, which reveals that I is a 3D supramolecular framework assembled by the intermolecular hydrogen bonds. Moreover, the magnetic studies of I showed that there exist antiferromagnetic interactions between the Gd(III) centres. The unit cell parameters for I: a = 33.453(3), b = 10.5469(10), c = 18.7895(18) Å, β = 123.7670(10)°, V = 5511.0(9) Å3, Z = 8.

A new coordination polymer Mn2(L)(DMF)2(H2O)2 (I), H4L = 2,3′,5,5′-biphenyl tetracarboxylic acid has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The X-ray diffraction analysis shows that I (C22H20Mn2N2O12) crystallizes in the monoclinic crystal system space group P21. The magnetic studies of I showed that there exist antiferromagnetic interactions between the Mn(II) centres. The unit cell parameters for I: a = 9.6271(13), b = 13.1172(17), c = 10.5726(14) Å, β = 110.084(2)°, V = 1253.9(3)Å3, Z = 2.

Two series of lanthanide–organic frameworks with the formulas [Ln(BTATB)(DMF)2(H2O)]·DMF·2H2O (Ln = La (1a), Eu (2a), Tb (3a), Er (4a)) and [Ln(BTATB)(H2O)2]·2DMA·4H2O (Ln = Er (1b), Yb (2b), Lu (3b)), respectively, were solvothermally synthesized from 4,4′,4″-(benzene-1,3,5-triyltris(azanediyl))tribenzoate (H3BTATB) and Ln(NO3)3 under DMF or DMA media and characterized by thermogravimetric analyses, IR spectroscopy, X-ray powder diffraction, and single crystal X-ray diffraction. X-ray single-crystal diffraction analyses for these complexes revealed that series A features an interesting 2D interdigitated layer architecture with (6,3) topology. Series B exhibits a 2D bilayer structure. The luminescence properties were studied, and the results showed that complex 3a displayed strong fluorescent emission in the visible region, where the emission intensities of 3a are enhanced upon the addition of Zn2+, demonstrating Zn2+-modulated fluorescence. Yb(III) complex 2b emits typical near-infrared luminescence (983 nm) in DMF (λex = 315 nm). The Knoevenagel condensation reaction (benzaldehyde and malononitrile or ethyl cyanoacetate in acetonitrile) was studied using 3a and 2b as catalysts. The results showed that the conversion rates of reactions catalyzed by 3a increased to 99 and 42%, respectively, whereas the reactions catalyzed by 2b exhibited lower conversion rates.

Three dinuclear complexes with the formulas [Cd2(L1)4(DMF)2(H2O)2] (1), [Mn2(L1)4(DMF)2(H2O)2] (2), [Cu2(L2)4(EtOH)(H2O)] 2DMF (3) (L1 = 3-(anthraquinone-1-diyl) benzoate, L2 = 4-(anthraquinone-1-diyl)benzoate), have been successfully synthesized under solvothermal conditions. The characterization by thermogravimetric analysis, PXRD patterns and IR spectra of 1–3 was carried out. The oxidation state of the Mn(II) and Cu(II) atoms was confirmed by the magnetic studies. The Cu(II) complex has the activity for DNA cleavage. The supercoiled DNA was completely degraded to nicked DNA (72%) and linear DNA (38%) with 1 μg μL−1 Cu(II) complex for 2 h at pH 7.0. The DNA cleavage by the Cu(II) complex was likely to proceed via a hydrolytic degradation pathway.

The solvothermal reaction of 4,4′-(benzothiadiazole-4,7-diyl)dibenzoate and Zn(II) leads to the generation of an interdigitating three-dimensional (2D + 2D → 3D) porous metal–organic framework, which displays a highly selective fluorescent enhancement with Cd2+ amongst other metal ions.

A new metal-organic coordination polymer [Zn(Pydc)(Dppz)]n (I) (H2Pydc = 2,6-pyridinedicarboxylic acid, Dppz = dipyrido[3,2-a:2′,3′-c]phenazine) was hydrothermally synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group P21/c. The Pydc2− ligands adopt O,N,O′-tridentate chelating and monodentate bridging coordination mode to link two adjacent Zn2+ ions to form a one-dimensional (1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and π-π stacking interactions, forming a three-dimensional (3D) supramolecular framework. The unit cell parameters for I: a = 7.332(3) Å, b = 36.023(9) Å, c = 7.8838(13) Å, β = 105.65(3)○, V = 2005.1(10) Å3, Z = 4.

The title cobalt(II) coordination polymer, [Co(Atibdc)(Dpa)]n (I) (H2Atibdc = 5-amino-2,4,6-triiodoisophthalic acid, Dpa = 2,2′-dipyridylanine), has been synthesized under solvothermal conditions and characterized by elemental analysis, IR, and X-ray crystallography structural analysis. Complex I exhibits a one-dimensional chain structure in which 5-amino-2,4,6-triiodoisophthalate as a bridging ligand interconnects adjacent two Co(II) centers to form a helical chain structure. The asymmetric unit includes one Co(II) center, one atibdc ligand, and one Dpa ligand. Each Co(II) center is five-coordinated and surrounded by two nitrogen atoms and three oxygen atoms from one Dpa ligand and two individual Atibdc ligands, leading to distorted trigonal bipyramid geometry. Adjacent chains are further linked through hydrogen bonds, C-H-π and π-π stacking interactions to form a three-dimensional supramolecular framework.

A Mn(II)-based homometallic porous metal–organic framework, Mn5(btac)4(μ3-OH)2(EtOH)2·DMF·3EtOH·3H2O (1, btac = benzotriazole-5-carboxylate), has been solvothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, and X-ray crystallographic study. 1 is a 3D neutral framework featuring 1D porous channels constructed by {Mn–OH–Mn}n chains and btac linkers. Magnetic studies show that 1 is a 3D metamagnet containing 1D {Mn–OH–Mn}n ferrimagnetic chains. High-pressure H2 adsorption measurement at 77 K reveals that activated 1 can absorb 0.99 wt % H2 at 0.5 atm and reaches a maximum of 1.03 wt % at 5.5 atm. The steep H2 absorption at lower pressure (98.2% of the storage capacity at 0.5 atm) is higher than the corresponding values of some MOFs (MIL-100 (16.1%), MOF-177 (57.1%), and MOF-5 (22.2%)). Furthermore, activated 1 can adsorb CO2 at room temperature and 275 K. The adsorption enthalpy is 22.0 kJ mol–1, which reveals the high binding ability for CO2. Detailed gas sorption implies that the exposed Mn(II) coordination sites in the activated 1 play an important role to improve its adsorption capacities.

The reaction of Zn(II) and 4,4′,4′′-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))-tribenzoic acid (H3BBC) without or with the presence of 2-amino-1,4-benzenedicarboxylic acid (NH2-H2BDC) under solvothermal conditions leads to the generation of two novel Zn(II) coordination polymers, [Zn(BBC)(H2O)2](Me2NH2)·12DMF (1) and [Zn2(BBC)(NH2–BDC)](Me2NH2)·10DMF (2), which feature a 2D (6,3) net and a 3D three-fold interpenetrating (3,5)-connected network, respectively. The resulting crystals of 2 were not a racemic mixture but enantiomeric excess, which was confirmed by the measurement of optical rotation of bulk samples using the solid circular dichroism (CD) spectra based on large crystals from one crystallization. Two compounds exhibit strong photoluminescence in the solid state at room temperature.

The solvothermal reaction of Mn(II) and tri(2-carboxyethyl)isocyanurate (H3tci) with or without the presence of 1,2-bis(4-pyridyl)ethylene in different solvents leads to the generation of three novel Mn(II) coordination polymers, namely, Mn3(tci)2(DMF)2(H2O)2 (1), [Mn3(tci)2(DMA)4]·2DMA (2) and [Mn(Htci)(bpe)0.5]·H2O (3). 1 features a 3D porous coordination polymer constructed by {Mn–(μ2–O)–Mn}n chains linked by the flexible arms of tci ligands. 2 features a 2D CdI2 topological layer based on trinuclear Mn(II) clusters as nodes. 3 is a 3D pillar-layered structure. The magnetic properties of these complexes have also been reported.

The reaction of Cu(NO3)2·3H2O/Zn(NO3)2·6H2O and D-3-(4-Pyridyl)-alanine (Hpyala) without or with 4,4′-bipyridine (bpy) leads to the generation of two new coordination polymers, [Cu(pyala)2]·H2O (1) and [Zn(4-pyridylacrylate)2]·H2O (2). Interestingly, the 4-pyridyacrylate ligand was derived from the in situ deaminization of the D-3-(4-Pyridyl)-alanine under the hydrothermal conditions. Single-crystal X-ray diffraction studies indicate that 1 exhibits a one-dimensional (1D) chiral chain structure; 2 exhibits 3D framework with 5-fold interpenetrated diamondoid topology, which contains open channels occupied by the lattice water molecules.The reaction of Cu(NO3)2·3H2O/Zn(NO3)2·6H2O and D-3-(4-Pyridyl)-alanine (Hpyala) without or with 4,4’-bipyridine (bpy) leads to the generation of two new coordination polymers, [Cu(pyala)2]·H2O and [Zn(4-pyridylacrylate)2]·H2O. Interestingly, the 4-pyridyacrylate ligand was derived from the in situ deaminization of the D-3-(4-Pyridyl)-alanine under the hydrothermal conditions.Highlights► [Cu(pyala)2]·H2O(1) and [Zn(4-pyridylacrylate)2]·H2O(2) have been synthesized. ► 4-pyridylacrylate was in situ generated from D-3-(4-Pyridyl)-alanine. ► 1 exhibits a one-dimensional chiral chain structure. ► 2 is a 3D framework with 5-fold interpenetrated diamondoid topology.

Four new metal-organic coordination polymers, Cd(mip)(DMF)(1), Cd(mip)(EtOH)(2), Cd2(mip)2(H2O)5·3H2O (3), Cd(mip)(bpp)(H2O)·H2O (4) (H2mip = 5-methylisophthalic acid, bpp = 1,3-di(4-pyridyl)propane) have been hydro(solvo)thermally synthesized and characterized by IR, thermogravimetric (TG) analysis, powder X-ray diffraction and single-crystal X-ray diffraction. 1 and 2 are isostructural, and two adjacent Cd centers are bridged by four carboxylate groups in μ2-carboxylato-κ1O.:κ1O′ and μ2Ο; κ2O,O′ fashion to form a linear (Cd–O–Cd)n chain. The adjacent (Cd–O–Cd)n chains are further connected by mip bridges to form a 3D framework. 3 features two types of chiral layers: One left-handed and another right-handed, which lead to racemic solid-state compound. 4 exhibits a two-dimensional wave-like (2D) (4,4) layer structure with infinite 1D linear chain. In addition, the luminescent properties of 1–4 are also discussed.

A new coordination polymer [Cu(H2Tci)2(Bipy)(H2O)] · 2H2O (I) (H3Tci = tris(2-carboxyethyl)isocyanurate, Bipy = 4,4′-bipyridine) has been synthesized and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I (C34H42CuN8O21) crystallizes in the monoclinic crystal system, space group P21/c. In I, the metal centers are linked by Bipy ligands to generate an infinite linear chain and the H2Tci ligands adopt monodentate coordination mode to graft the linear chain. The adjacent chains are linked by hydrogen bonds to form a three-dimensional supramolecular framework.

A new coordination polymer, [(CH3)2NH2][Zn(Tci)] · 2.5H2O (I) (H3Tci = tris(2-carboxyethyl)isocyanurate), has been synthesized under solvothermal conditions. X-ray diffraction analysis reveals that I features a 2D anionic layer structure constructed by Zn(II) paddle-wheel building blocks and Tci linkers. The Zn(II) paddle-wheel can be viewed as a node, and the network of I can be simplicated as CdI2 net. Hydrogen bond interactions link the adjacent 2D layers to form a 3D supramolecular framework.

A new coordination polymer [Gd(Oba)(Ox)0.5(H2O)2]n (I) (H2Oba = 4,4′-oxybis(benzoic acid), H2Ox = oxalic acid) has been synthesized by hydrothermal reactions and characterized by elemental analysis and single-crystal X-ray diffraction. In I, two Gd3+ ions are bridged by Oba ligands to form 1D ribbon chains, which are further connected by Ox ligands, generating a 2D layer structure.

A new coordination polymer, [Cd(Oba)(TATP) · H2O(I) (Oba = anion of 4,4′-oxybis(benzoic acid), TATP = 1,4,8,9-tetranitrogen-trisphene), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, and single crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that I is an interesting 1D zigzag chain structure. The adjacent chains are further connected together via the strong π−π packing interactions and hydrogen bonding to form a 3D supramolecular framework.

A new one-dimensional (1D) zigzag chain coordination polymer [Co(Bpdc)(Dpa)]n (H2Bpdc = benzophenone-4,4′-dicarboxylic acid, Dpa = 2,2′-dipyridylanine) (I) has been synthesized under solvothermal conditions and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group P21/c. The unit cell parameters for I: a = 12.586(1), b = 15.3415(1), c = 11.345(1) β = 91.719(7)°, V = 2173.1(3) Å3, Z = 4.

The solvothermal reaction of In(III) and 1,2,4,5-benzeneteracarboxylic acid with the presence of piperazine leads to the generation of a novel 3D chiral porous coordination polymer with PtS topological net. Interestingly, the resulting crystals were not a racemic mixture but enantiomeric excess, which was confirmed by the measurement of optical rotation of bulk samples using solid vibrational circular dichroism (VCD) spectra and the solid circular dichroism (CD) spectra based on large crystals from one crystallization. High-pressure CO2 and CH4 adsorption measurement at 298 K reveals that activated 1 can absorb 45.8 cm3 (STP)/g CO2 at 22 atm and 22.5 cm3 (STP)/g CH4 at 25 atm.

Reaction of Zn(OAc)2·2H2O and bis(2-carboxyethyl)isocyanurate (H3bci) leads to the generation of a new coordination polymer, Zn(Hbci)(H2O)3 (1), (H3bci = bis(2-carboxyethyl)isocyanurate), which features an interesting 2D layer containing Zn(II)–Hbci–Zn(II) right-handed and left-handed helical chains and μ2-H2O bridges. Furthermore, hydrogen bonds link the adjacent 2D layers to form a 3D supramolecular framework. The photoluminescence property of 1 was also studied.Graphical abstractReaction of Zn(OAc)2·2H2O and bis(2-carboxyethyl)isocyanurate (H3bci) leads to the generation of a new coordination polymer, Zn(Hbci)(H2O)3 (1), (H3bci = bis(2-carboxyethyl)isocyanurate), which features an interesting 2D layer containing Zn(II)–Hbci–Zn(II) right-handed and left-handed helical chains and μ2-H2O bridges.

A new coordination polymer [Cd2(cpta)(H2O)4]n (1) (H4cpta = cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid) has been hydrothermally synthesized and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 is a six-connected pcu-type network with (41263) topology. 1 also displays strong fluorescent emissions in the solid state at room temperature.A new 3D 6-connected coordination polymer with 41263 topology, [Cd2(cpta)(H2O)4]n (H4cpta = cis,cis,cis-1,2,3,4-cyclopentanetetra carboxylic acid), has been synthesized under hydrothermal synthesized using H4cpta as linear linkers and Cd4-clusters as 6-connected nodes.Research Highlights► Recently, a large number of organic ligands as potential linkers, polynuclear coordination polymers consisting polycarboxylate ligands have witnessed the most important development. ► To the best of our knowledge, complexes based on cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic ligand have rarely been reported, maybe due to its versatility and flexibility in binding fashions when forming coordination architectures, although the rigid tetracarboxylate ligand, benzene-1,2,4,5-tetracarboxylic acid, has been widely investigated. ► In this study, we select cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid considering its following several feature: (a) it has four carboxyl groups that provide versatile binding fashions; (b) In view of the number of deprotonated carboxyl groups, it can behave not only as hydrogen-bond acceptor but as hydrogen-bond donor; (c) It connects the metal ions in various directions, because all carboxyl groups do not lie in one plane. In this paper, we report the synthesis, crystal structure, and photoluminescence of a new [Cd2(cpta)(H2O)4]n(1), which features an interesting 3D coordination polymer.

Ionothermal reaction of isophthalate (H2ip), and colbolt(II) nitrate under 1-ethly-3-methylimidazolium bromide (EMimBr) as solvent leads to a novel three dimensional metal–organic framework (EMim)2[Co3(ip)4] (1). It can be described as an eight-connected CsCl-type net (42464) utilizing trinuclear Co(II) clusters as eight-connected nodes and ip ligands as linkers. The imidazolium cation [EMim]+ of the ionic liquid acting as charge-compensating agents has interactions with the framework. The magnetic properties studies show ferrimagnetic behavior for 1.Ionothermal reaction of isophthalate and Co(II) leads to the generation of a three dimensional complex, (EMim)2[Co3(ip)4]. It can be described as a eight-connected CsCl-type net based on trinuclear Co(II) clusters as eight-connected nodes and ip ligands as linkers. The magnetic properties studies show ferrimagnetic behavior.Highlights► A 3D complex (EMim)2[Co3(ip)]4 has beeen synthesized under ionothermal conditions. ► It can be described as a CsCl-type net based on trinuclear Co(II) clusters as nodes. ► The imidazolium cation has strong interaction with the framework.

A new 1D chiral metal-organic coordination polymer [Cu(Cphe)2] · 3H2O (I) (HCphe = L-3-Cyanophenylalanine) has been synthesized in an aqueous solution and characterized by elemental analysis, thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD), infrared spectroscopy (IR) and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic space group P21. The adjacent copper(II) atoms are linked by Cphe ligands to form a 1D zigzag chain, which is further connected via strong hydrogen bonds to form a 3D supramolecular framework. The unit cell parameters for I are: a = 12.0201(8), b = 6.1495(4), c = 14.8576(10) Å, β = 94.1720(10)°, V = 1095.00(13) Å3, and Z = 2.

A new coordination polymer (H3O+)[In(Tbip)2] · H2O (I) (H2Tbip is 5-tert-butylisophthalic acid) has been synthesized under hydrothermal conditions. Complex I has been characterized by elemental analysis, IR, TG analysis, and powder X-ray diffraction. Single-crystal X-ray diffraction studies revealed that I crystallizes in the monoclinic crystal system, space group C2/c. In I the metal centers are linked by bridging Tbip ligand to form an interesting extended two-dimensional rhombic network.

A new chiral coordination polymer [Cd2(C4H4O6)2]n (I) has been synthesized and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the orthorhombic system, space group P212121. The adjacent Cd(1) and Cd(2) centers are linked by one tartrate ligand through tridentate coordination to form a dimer. The dimer is further connected to the other dimer via tartrate ligands to construct an infinite three-dimensional (3D) coordination polymer. The unit cell parameters for I: a = 7.4984(17), b = 7.9106(18), c = 19.560(4) Å, V = 1160.2(5) Å3, Z = 4.

A new metal-organic coordination polymer, namely [Ni(1,4-BDC)(N-MIM)2]n (I) (1,4-BDC = 1,4-benzenedicarboxylic acid and N-MIM = N-methylimidazole), has been synthesized under solvothermal conditions by using N-MIM as solvent and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group C2/c. The 1,4-BDC ligand adopts a bis(bidentate) chelating mode to connect two adjacent Ni(II) centers to form a one-dimensional (1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and π-π stacking interactions, forming a three-dimensional (3D) supramolecular framework. The unit cell parameters for I: a = 17.250(10), b = 7.214(4), c = 16.506(7)Å, β = 125.53(4)°, V = 1671.6(15)Å3, Z = 4.

A new coordination polymer, [Zn(Btca)(Phen)]n (I) (H2Btca = benzotriazole-5-carboxylic acid, Phen = 1,10-phenanthroline), has hydrothermally been synthesized by the reaction of zinc nitrate, H2Btca and Phen in the presence of DMF and H2O. Single-crystal X-ray diffraction analysis reveals that in complex I the metal centers are linked by the bridging Btca ligand to form an extended two-dimensional wave-like layer decorated by Phen.

A new coordination polymer, [Co(Atibdc)(Bipy)(H2O)3] · 2DMF · H2O (I) (H2Atibdc = 5-amino-2,4,6-triiodoisophthalic acid, Bipy = 4,4′-bipyridyl), has been synthesized and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I (C24H30CoI3N5O10) crystallizes in the monoclinic system, space group P21/n. The adjacent cobalt atoms adopt different coordination modes via nitrogen atoms from two different Bipy ligands to generate an infinite linear chain, which are further linked by hydrogen bonds and I…I weak interactions to form a two-dimensional layer.

A new one-dimensional (1D) zigzag chain coordination polymer [Zn(ATIBDC)(DPA)]n (H2ATIBDC = 5-amino-2,4,6-triiodoisophthalic acid, DPA = 2,2′-dipyridylamine) has been synthesized under solvothermal conditions and characterized by elemental analysis, IR, and single-crystal X-ray diffraction.

The anionic CdI2-type topological net, [Cu2(tci)2]2−, and the pentanuclear copper cluster cation [Cu5(tci)2(OH)2(H2O)8]2+ [tci = tris(2-carboxyethyl)isocyanurate] form a complementary 3D supramolecular framework. Interestingly, there exist centrosymmetric cyclic (H2O)18 clusters in the cavities.

A solvothermal reaction of Zn(OAc)2, 4,4′-bipyridine (bpy) and tri(2-carboxyethyl)isocyanurate (H3tci) in presence or absence of NaOH leads to the generation of two novel coordination polymers, [Zn3(tci)2(bpy)1.5(H2O)2]·6H2O (1) and [ZnNa(tci)(bpy)0.5(H2O)]·2H2O (2), which feature a three-fold interpenetrating (3,4,5)-connected 3D network and a two-fold interpenetrating (4,5)-connected (43.63)(43.66.8)-fsx network, respectively.

A novel coordination polymer, [In(Pdc)(OH)(Bipy)]n(I) (H2Pdc is 3,5-pyridinedicarboxylic acid, Bipy is 2,2′-bipyridine), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the triclinic crystal system, space group P\( \bar 1 \) and features an interesting 1D linear chain structure, which contains dinuclear [In2(Pdc)2(Bipy)2] subunits. The cell unit parameter for I: a = 8.629(1), b = 9.802(2), c = 10.227(2) Å, α = 79.20 (1)°, β = 76.08(1)°, γ = 71.44 (1)°, and Z = 2.

The hydrothermal reaction of Co(II)/Cu(II), 5-hydroxyisophthalic acid and dipyridophenazine leads to the generation of two 3D chiral coordination polymers, [M(hip)(DPPZ)]n (M = Co(1), Cu(2), H2hip = 5-hydroxyisophthalic acid, DPPZ = dipyridophenazine), which contain M-hip-M helical chains (M = Co, Cu) and possess a new four-connected 66 topological net. The resulting crystals were not a racemic mixture but an enantiomeric excess, which was confirmed by the measurement of optical rotation of the bulk samples using solid state vibrational circular dichroism (VCD) and solid circular dichroism (CD) based on the large crystals from one crystallization. The magnetic properties of 1 and 2 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that antiferromagnetic interactions exist in 1 and 2.

By control of mixed ligands with particular coordination sites, heterometallic coordination polymers, [Ln2(H2O)2Ag(C2O4)2(ina)3]n (Ln = Eu (1), Dy (2), Hina = isonicotinic acid) and {[LnAg(C2O4)(na)2]·2H2O}n (Ln = La (3), Tb (4), Hna = nicotinic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. These coordination polymers feature 3D pillar-layered coordination frameworks constructed from two-dimensional (2D) lanthanide–carboxylate layers and Ag(ina) or Ag(na) pillars. It is interesting that the in situ decarboxylation of pyridine-2,3-dicarboxylic acid into nicotinic acid was observed. The luminescent properties of 1 and 4 were also studied.Heterometallic coordination polymers, [Ln2(H2O)2Ag(C2O4)2(ina)3]n (Ln = Eu, Dy, Hina = isonicotinic acid) and {[LnAg(C2O4)(na)2]·2H2O}n (Ln = La, Tb, Hna = nicotinic acid), have been synthesized under hydrothermal conditions. These coordination polymers feature 3D pillar-layered coordination frameworks constructed from two-dimensional lanthanide–carboxylate layers and Ag(ina) or Ag(na) pillars.

Three lanthanide coordination polymers, [Ln(Hpdc)(ox)0.5(H2O)2]·H2O (Ln = Nd(1), Eu(2), Er(3)) (H3pdc = 3,5-pyrazoledicarboxylic acid, ox = oxalate), have been synthesized by the hydrothermal reaction of lanthanide nitrates, 3,5-pyrazoledicarboxylic acid, and oxalic acid (H2ox) and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that complexes 1–3 are isomorphous and exhibit three-dimensional metal–organic frameworks with uncommon (4,5)-connected topology, which contain open channels occupied by the lattice water molecules. The photoluminescent properties of complex 2 were also studied.Three lanthanide coordination polymers, [Ln(Hpdc)(ox)0.5(H2O)2]·H2O (Ln = Nd(1), Eu(2), Er(3)) (H3pdc = 3,5-pyrazoledicarboxylic acid, ox = oxalate), have been synthesized by the hydrothermal reaction of lanthanide nitrates, 3,5-pyrazoledicarboxylic acid, and oxalic acid (H2ox) and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that complexes 1–3 are isomorphous and exhibit three-dimensional metal–organic frameworks with uncommon (4,5)-connected topology.

A new metal-organic network (EMIM)[Co2(hip)2(μ3-OH)]·H2O (1), (H2hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been synthesized by the ionothermal reaction of cobalt nitrate, H2hip and [EMIM]Br ionic liquid. Single-crystal X-ray diffraction analysis reveals that 1 exhibits a two-dimensional (2D) bilayer constructed from tetranuclear [Co4(μ3-OH)2] building units and hip2− linkers. There are square cavities with the dimension of 10.161 × 10.868 Å. The [EMIM]+ cations are located in the cavities, which have the hydrogen bonding interactions with the bilayer. Further more, the strong hydrogen bonds between the carboxylate and hydroxyl oxygen atoms of hip2− ligands and lattice water molecules extend the 2D layer into a 3D supramolecular network. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that there exist antiferromagnetic interactions.A new metal-organic framework, (EMIM)[Co2(hip)2(μ3-OH)] (1), (H2hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been ionothermally synthesized and exhibits a two-dimensional bilayer structure constructed from tetranuclear [Co4(μ3-OH)2] building units and hip linkers. The imidazolium cations [EMIM]+ acting as solvent and charge compensating agent located in the cavities of the bilayer framework.

Two new vanadium tellurites, Cu(TATP)V2TeO8(1) and Cu(DPPZ)V2Te2O10(2), (TATP=1,4,8,9-tetranitrogen-trisphene, DPPZ=dipyridophenazine) have been synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR, and single-crystal X-ray diffraction. Compound 1 features an interesting two-dimensional layer structure constructed by [V2TeO8]n double-chain-like ribbons linked by [Cu(TATP)]2+ bridges. Compound 2 consists of two types of chiral layers: one left-handed and the other right-handed, which lead to racemic solid-state compound. In each layer, there exist two types of inorganic helical chains (V4Te4O8)n and (Te2O2)n, with same handedness. Two types of helical chains are linked by μ3(O6) atoms to generate a V/Te/O inorganic anionic layer. The [Cu(DPPZ)]2+ cationic complex fragments are covalently bonded to the layer, projecting below and above the vanadium tellurites layer.The changes of the size of the rigid aromatic chelate ligands may influence the structures of the V–Te–O framework.

The hydrothermal reaction of In3+ and 1,2,4-benzenetricarboxylic acid with the presence of piperazine leads to the generation of a novel 3D porous coordination polymer, [H3O][In2(btc)(bdc)(OH)2]·5.5H2O (1), (btc=1,2,4-benzenetricarboxylate, bdc=1,4-benzenedicarboxylate). Compound 1 crystallizes in orthorhombic space group Pbca with a=16.216(7) Å, b=13.437(6) Å, c=31.277(14) Å, and Z=8. It is interesting to find that the in-situ decarboxylation reaction of 1,2,4-benzenetricarboxylate (btc) partially transformed into 1,4-benzenedicarboxylate (bdc) occurs. The 16 indium(III) centers were linked by four btc, four bdc and two μ2-OH ligands to form a box-girder. The adjacent box-girders are further connected by the bdc and btc ligands to generate a novel porous metal–organic framework containing nanotubular open channel with a cross-section of approximately 11.5×11.3 Å2. The micropores are occupied by lattice water molecules, and the solvent-accessible volume of the unit cell was estimated to be 3658.6 Å3, which is approximately 53.7% of the unit-cell volume (6815.4 Å3).The hydrothermal reaction of In3+ and 1,2,4-benzenetricarboxylic acid with the presence of piperazine leads to the generation of a novel 3D porous coordination polymer, [H3O][In2(btc)(bdc)(OH)2]·5.5H2O, (btc=1,2,4-benzenetricarboxylate, bdc=1,4-benzenedicarboxylate).

To investigate the influence of the size of aromatic chelate ligands on the frameworks of metal dicarboxylate polymers, two one-dimensional coordination compounds [Cu(BDC)(TATP)(H2O)]n (I) and [Cu(BDC)(DPPZ)]n (II), (BDC = 1.4-benzenedicarboxylate, TATP = 1,4,8,9-tetranitrogentrisphene, DPPZ = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized under similar conditions and structurally characterized by X-ray crystallography. Compounds I and II have the similar zigzag chain structure, but the substitution of TATP with DPPZ results in the difference of the degree of bending of the chain, indicating that the sizes of the rigid aromatic chelate ligands have important effect on the structures of their complexes.

A new complex [Zn2(Pydc)2(Bipy)(H2O)8] (I) (H2Pydc = 2,5-Pyridinedicarboxylic Acid, Bipy = 4,4′-bipyridine) was hydrothermally synthesized and characterized by elemental analyses and single crystal Xray diffraction. The X-ray diffraction analysis reveals that I is a discrete binuclear Zn(II) complex and the adjacent binuclear units are further connected together via the strong H-bonding interactions.

Two one-dimensional coordination polymers, [Cu(Oba)(TATP)]n · nH2O (I) and [Cu(Oba)(DPPZ)(H2O)]n · nH2O (II) (Oba is 4.4′-oxy-bis(benzoate), TATP is 1,4,8,9-tetranitrogen-tris(phene), DPPZ is dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized under similar conditions and structurally characterized by elemental analysis, IR spectra, and X-ray crystal structure. Compounds I and II are based on topologically identical chains, where the copper centers chelated by the amine ligands are linked by the Oba bridges, as well as the coordination modes of the Oba ligands. However, the angles between the individual links and the environment of the copper centers are substantially different between the two compounds and were found to be primarily influenced by the sizes of the rigid aromatic chelate ligands.

Two new coordination polymers, (EMIM)2[M(Pydc)2] (M is Co, Zn; EMIM is 1-ethyl-3-methylimidazolium; H2Pydc is 2,5-pyridinedicarboxylic acid), have been synthesized through the reaction of cobalt or zinc nitrate with H2Pydc in the ionic liquid medium. The structures exhibit a two-dimensional 4.4-network with the imidazolium cations, acting as charge compensating agent, located between the layers of the coordination anion polymeric frameworks.

A new 3D coordination polymer, [LaAg(Pydc)(HPydc)(C2O4)0.5(H2O)2]n (I) (H2Pydc = pyridine-3,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C15H11AgLaN2O12) crystallizes in triclinic space group P\( \bar 1 \) and features an interesting 3D framework constructed by 2D layers via strong Ag-Ag interactions. Unit cell parameters for I (n = 1): a = 7.749(2), b = 8.316(1), c = 14.239(3) Å, α = 97.64(2)°, β = 100.12(2)°, γ = 94.37(2)°, and Z = 2.

A new 1D coordination polymer, [Cd(pydc)(phen)]n (1) (pydc = pyridine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline), has been hydrothermally synthesized and characterized by the elemental analysis, IR spectroscopy and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 (C19H11CdN3O4) crystallizes in triclinic space group P-1, features an interesting 3D zipper-like network constructed from 1D ribbons via π–π stacking interactions. Unit cell parameters for 1: a = 7.681(1) Å, b = 10.546(2) Å, c = 11.358(2) Å, α = 107.12(2)°, β = 99.50(2)°, γ = 109.12 (2)° and Z = 2.

A new indium(III) coordination polymer [In(OH)(Hpdc)(H2O)]n (1) H3pdc = 3,5-pyrazole-dicarboxylic acid) has been synthesized under hydrothermal condition and characterized by the elemental analysis and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 (C5H5InN2O6) crystallizes in the monoclinic space group P21/n, and features an interesting 2D layer constructed by 1D In–Hpdc chains and μ2-OH ligands. Unit cell parameters for 1: a = 10.406(2), b = 6.326(2), c = 11.631(2) Å, β = 104.0(1)°, and Z = 4.The title compound, [In(OH)(Hpdc)(H2O)]n (H3pdc = 3,5-pyrazole-dicarboxylic acid), was synthesized under hydrothermal condition by the treatment of InCl3·4H2O with 3,5-pyrazole-dicarboxylic acid and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the molecular structure of the title compound is an interesting 2D layer constructed by 1D In–Hpdc chains and μ2-OH ligands.

A new 3D coordination polymer, [Cd(pzdc)(bpy)]n (1) (pzdc = pyrazine-2,3-dicarboxylic acid, bpy = 2,2′-bipyridine), has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 (C16H10CdN4O4) crystallizes in monoclinic space group P21/c, features an interesting 3D zipper-like networks constructed by 2D layers via strong π–π packing interactions. Cell unit parameter for 1: a = 9.767(1), b = 14.022(2), c = 13.719(2) Å, β = 100.86(1)o, and Z = 4.A new 3D coordination polymer, [Cd(pzdc)(bpy)]n (pzdc = pyrazine-2,3-dicarboxylic acid, bpy = 2,2′-bipyridine), has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum and single crystal X-ray diffraction. X-ray diffraction analysis reveals that [Cd(pzdc)(bpy)]n features an interesting 3D zipper-like networks constructed by 2D layers via strong π–π packing interactions. Open image in new window

A new coordination polymer, [Zn(Pydc)(Tapt)]n (I) (H2Pydc = 2,6-Pyridinedicarboxylic acid, Tapt = 1,4,8,9-tetranitrogen-trisphene), was hydrothermally synthesized and characterized by elemental analyses and single-crystal X-ray diffraction, which revealed that I has an interesting 1D chain structure; the adjacent chains are further connected together via the strong π-π packing interactions.

The solvothermal reaction of Zn(II) and 4,4′-oxybis(benzoic acid) in the presence of anhydrous ethanol leads to the generation of a novel 3D chiral coordination polymer with triple helical chains; the resulting crystals were not a racemic mixture but had an enantiomeric excess, which was confirmed by measuring the optical rotation of bulk samples using solid state vibrational circular dichroism (VCD).

The hydrothermal reaction of Cu(NO3)2, isophthalate (ip) and 2,2′-bipyridine (2,2′-bpy) without or with K2Cr2O7 affords different complexes, whose structures are controlled only by the addition of the K2Cr2O7. The reaction of Cu(NO3)2, isophthalate and 2,2′-bipyridine yields a novel one-dimensional double-chain coordination polymer [Cu3(ip)2(Hipa)2(bpy)2]n (1). However, with the addition of K2Cr2O7 in the above reaction at the same hydrothermal conditions, a discrete hexanuclear Cu(II) complex [Cu6(ipO)4(2,2′-bpy)2(H2O)2]·6H2O (2) (ipOH = 2-hydroxyisophthalate) was isolated. It is interesting to find that the in situ reaction of isophthalate (ip) oxidized to 2-hydroxyisophthalate (ipOH) occurs. K2Cr2O7 acts as an oxidant. The magnetic properties of 1 and 2 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that intramolecular ferromagnetic interactions exist with weak intermolecular antiferromagnetic interactions at very low temperature in 1 and weak antiferromagnetic interactions admixture with strong ferromagnetic interactions in 2.

Two new CuI coordination polymers, [CuI(TATP) (CN)]n (1) and [CuI(bpy)(SCN)]n (2) (TATP = 1,4,8,9-tetranitrogen-trisphene, bpy = 2,2′-bipyiridine), have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, and X-ray crystallography. In 1 and 2, the metal centers are linked by bridging CN−/SCN− to form one-dimensional chains in the crystals and are stabilized by interchain π–π stacking interaction.

A metal-organic framework, [Co2(pydc)2(bpy)2]n · 2nH2O (1) (H2pydc = pyridine-3,4-dicarboxylic acid, bpy = 4,4′-bipyridine), was synthesized under hydrothermal conditions. X-ray diffraction experiments reveal that (1) exhibits a chiral 3D metal-organic framework, which represents the rare example of 3D chiral coordination polymers containing two kinds of organic ligands. Temperature-dependent magnetic susceptibility for (1) was also studied.

The solvothermal reaction of Zn(II) and 4,4′-oxybis(benzoic acid) in the presence of anhydrous ethanol leads to the generation of a novel 3D chiral coordination polymer with triple helical chains; the resulting crystals were not a racemic mixture but had an enantiomeric excess, which was confirmed by measuring the optical rotation of bulk samples using solid state vibrational circular dichroism (VCD).

Two series of chemically and thermally stable rare-earth MOFs were constructed using trinuclear [M3(μ3-OH)(COO)6] SBUs and linear dicarboxylate linkers, which feature three-dimensional 12-connected frameworks with an hcp topology. These materials contain a large density of Lewis acidic sites, leading to high catalytic activity towards the cycloaddition of CO2 and epoxides under mild conditions.

The solvothermal reaction of In(III) and 1,2,4,5-benzeneteracarboxylic acid with the presence of piperazine leads to the generation of a novel 3D chiral porous coordination polymer with PtS topological net. Interestingly, the resulting crystals were not a racemic mixture but enantiomeric excess, which was confirmed by the measurement of optical rotation of bulk samples using solid vibrational circular dichroism (VCD) spectra and the solid circular dichroism (CD) spectra based on large crystals from one crystallization. High-pressure CO2 and CH4 adsorption measurement at 298 K reveals that activated 1 can absorb 45.8 cm3 (STP)/g CO2 at 22 atm and 22.5 cm3 (STP)/g CH4 at 25 atm.

MOF-templated nitrogen-doped porous carbon materials (NPCs) have been prepared by employing the previously reported MOF, [(CH3)2NH2]6[Ni(H2O)6]3{Ni6(η6-TATAT)4(H2O)12}, as a precursor, which can act as efficient electrocatalysts for oxygen reduction reactions (ORRs). The carbonized MOF acts as the carbon source, and urea is employed as an additional nitrogen source. The urea modified carbon materials, carbonized at 800 °C, 900 °C and 1000 °C under Ar atmosphere, all show electrocatalytic activity for ORRs; the material carbonized at 900 °C exhibits a more appropriate nitrogen content, robust pore structure and an excellent degree of graphitization. In alkaline media, NPC-900 exhibits superior catalytic activity (the onset and half-wave potentials are −0.06 V and −0.23 V vs. Ag/AgCl, respectively), excellent long-term durability and outstanding methanol tolerance compared with the commercial Pt/C catalyst.

An InIII-based anionic framework (InIII-MOF) with 4-connected SrAl2 topology was constructed. The InIII-MOF with permanent porosity functions as a host for encapsulation of Ln3+ ions through ion-exchange processes. The photophysical properties of the as-prepared Ln3+@InIII-MOF were investigated and the results showed that the InIII-MOF could serve as an antenna to sensitize Ln3+ cations, especially suitable for Tb3+ and Eu3+ ions. The possible sensitization mechanism has been studied by surface photovoltage spectroscopy. Additionally, the InIII-MOF could also act as a host material when applied in the separation and purification of cationic dyes, which is highly based on the size and charge of organic dyes. Moreover, it can be used as a chromatographic column stationary phase to separate cationic dyes more efficiently and selectively. It is believed that the as-prepared InIII-MOF may have potential applications in optical materials and environmental fields.

The hydrothermal reaction of Co(II)/Cu(II), 5-hydroxyisophthalic acid and dipyridophenazine leads to the generation of two 3D chiral coordination polymers, [M(hip)(DPPZ)]n (M = Co(1), Cu(2), H2hip = 5-hydroxyisophthalic acid, DPPZ = dipyridophenazine), which contain M-hip-M helical chains (M = Co, Cu) and possess a new four-connected 66 topological net. The resulting crystals were not a racemic mixture but an enantiomeric excess, which was confirmed by the measurement of optical rotation of the bulk samples using solid state vibrational circular dichroism (VCD) and solid circular dichroism (CD) based on the large crystals from one crystallization. The magnetic properties of 1 and 2 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that antiferromagnetic interactions exist in 1 and 2.

The hydrothermal reaction of Cu(NO3)2, isophthalate (ip) and 2,2′-bipyridine (2,2′-bpy) without or with K2Cr2O7 affords different complexes, whose structures are controlled only by the addition of the K2Cr2O7. The reaction of Cu(NO3)2, isophthalate and 2,2′-bipyridine yields a novel one-dimensional double-chain coordination polymer [Cu3(ip)2(Hipa)2(bpy)2]n (1). However, with the addition of K2Cr2O7 in the above reaction at the same hydrothermal conditions, a discrete hexanuclear Cu(II) complex [Cu6(ipO)4(2,2′-bpy)2(H2O)2]·6H2O (2) (ipOH = 2-hydroxyisophthalate) was isolated. It is interesting to find that the in situ reaction of isophthalate (ip) oxidized to 2-hydroxyisophthalate (ipOH) occurs. K2Cr2O7 acts as an oxidant. The magnetic properties of 1 and 2 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that intramolecular ferromagnetic interactions exist with weak intermolecular antiferromagnetic interactions at very low temperature in 1 and weak antiferromagnetic interactions admixture with strong ferromagnetic interactions in 2.