The assembly of enantiopure tetrazoles with cupric ion gives rise to five homochiral zeolitic tetrazolate frameworks with rich topological nets, in which similar enantiopure porphyrin-like Cu(5-eatz)2 subunits (SBUs) are captured in situ and play different roles.

By mixing amino acids and tetrazolate ligands, a series of homochiral zeolitic metal–organic frameworks (ZMOFs) with ABW topology have been synthesized, and these materials show permanent microporosity and potential enantioselective recognition ability.

•A two-dimensional structure Zn4(5-mtz)4(l-malic)2(H2O)2 (1) has been hydrothermally prepared.•Tetrazolate shows imidazolate coordination mode and has uncoordinated N atoms acting as hydrogen-bonding acceptors.•Rich H-bond network is formed in adjacent layers.A two-dimensional structure Zn4(5-mtz)4(l-mal)2(H2O)2 (1, 5-mtz = 5-methyltetrazole, l-mal = l-malic acid) has been hydrothermally prepared and characterized by powder and single crystal X-ray diffraction, thermogravimetric (TG) analyses and IR spectroscopy. The 5-mtz and l-malic acid ligands connect the Zinc atoms to form two kinds of 1D chains, [Zn-5-mtz]n chain and [Zn-l-mal]n chain. These chains crosslink each other by sharing the Zn atoms to form the layer structure. Rich H-bond network is formed by H-bond interaction between coordinated water and uncoordinated N atoms of 5-mtz in adjacent layers. The proton conductivity of 1 was 1.33 × 10− 5 S cm− 1 at 60 °C under 95% RH. This indicates that 1 is a potential candidate material for proton conductivity.A new MOF material with rich H-bond network is synthesized by using l-malic acid and 5-methyl-1H-tetrazole as dual ligands. The proton conductivity was 1.33 × 10− 5 S cm− 1 at 60 °C under 95% RH, which indicates that this material is a potential candidate material for proton conductivity.Download high-res image (307KB)Download full-size image

Mixed 2-(1-hydroxy-ethyl)-3H-benzoimidazole-5-carboxylic acid and tetrazole ligands were used to synthesize three new zeolite-like metal–organic frameworks with diverse structures, and the resulting compound 2 shows high chemical stability and high CO2 uptake capacity.

Three tetrahedral tetrazolate frameworks (TTFs) with SOD, srs and ctn topologies (TTF-4, -5 and -6) are obtained by using the anion and solvent as structure-directing agents. The resulting SOD-type TTF-4 shows high chemical stability as well as high CO2 uptake capacity.

Catenation based on homochiral metal–organic nanocages or nanotubes is realized in this work for the first time. A flexible enantiopure ligand is employed to assemble metal ions, with the structure-directing effect of an auxiliary ligand, a triangular-prism-like nanocage, and a nanotube successfully built. Further 0D → 3D catenation is achieved by interlocking the nanocages, and 1D → 3D catenation based on nanotubes is also presented. This work reveals extraordinary catenating architectures from molecular cages and tubes.

An enantipure (1S)-1-(5-tetrazolyl)ethylamine (5-eatz) ligand was first employed to construct a homochiral porous metal–organic framework, {[CuI2CuII(5-eatz)2(CN–)(H2O)]+[NO3–]}·[DMF] (1), with unusual ligand-unsupported Cu···Cu interactions. Such a compound shows high stability in water and common organic solvents. Remarkably, it has high enantioselectivity toward (R,S)-1-phenylethanol and (R,S)-1-phenylpropanol with enantiomeric excess values of up to 42% and 48%, respectively.

Presented here is an interpenetrated three-dimensional copper–iodine cluster-based framework with dia topology based on two different kinds of Cu4I4 subunits that is templated by an enantiopure porphyrin-like CuI(5-eatz)2 unit and shows excellent photocatalytic activity to degrade methylene blue under visible light.

Presented here are two zeolitic tetrazolate-imidazolate frameworks (ZTIFs) with SOD and cag topologies (ZTIF-6 and -7) directed by link–link interaction. Furthermore, the SOD-type ZTIF-6 shows high chemical stability and permanent porosity, as well as selective separation of C2 hydrocarbons over C1 methane.

A new pillared-layer metal–organic framework [Zn2(NH2-BTB)(2-nim)] (1) was successfully synthesized based on mixed ligands, where binuclear [Zn2(CO2)3]+ cluster-based cationic layers [Zn2(NH2-BTB)]+ (NH2-H3BTB = 1,3,5-(three-benzoic acid)aniline) are connected by 2-nitroimidazoles. Compound 1 shows high uptake and good adsorption selectivities for C3/C1 and C2/C1. Particularly, the C2H2 uptake capacity of 1 is up to 152 cm3 g−1 at 273 K and the selectivity for C3H8/CH4 is over 85 at room temperature.

Before this work, adding chiral C centers into zeolitic imidazolate frameworks (ZIFs) has never been realized. Presented here are the first examples on achieving bulky homochirality in ZIF systems, and three homochiral zeolitic imidazolate-related frameworks with sodalite and dia topologies are successfully synthesized by employing enantiopure imidazolate derivatives. The results open a new blueprint on the synthetic design of homochiral ZIFs for future applications.

Presented here is an unusual microporous metal–organic framework (FIR-30) integrating helical channels, intrinsical chirality, and permanent porosity. The structure of FIR-30 containing three types of cages has two interpenetrating helical channel systems with opposite handedness, which can be considered a surface with the same topology as gyroid, and the generation of chirality is related with the intrinsically chiral topology of FIR-30. The results provide new insight toward the construction of chiral MOFs with helical channels.

Two enantiomorphic metal–organic frameworks with zeotype SOD topology have been successfully synthesized from enantiopure l-alanine and d-alanine, respectively, which demonstrates the feasibility of fabricating MOFs that integrate the 4-connected zeotype topologies and homochiral nature by the employment of enantiopure amino acids.

A porous 3D framework based on [Co2(μ2-OH2)] clusters and mononuclear Co centers, is presented. The [Co2(μ2-OH2)] units act as 7-connected and 8-connected nodes, respectively. The desolvated form of 1 shows high CO2 and H2 adsorption.

•A new three-dimensional zinc(II) isonicotinic complex was synthesized.•The compound exhibited threefold interpenetrated of diamond topological net.•The compound showed strong blue photoluminescence.A new 3D metal–organic framework, [Zn3(IN)6]⋅DMF⋅H2O (1, H-IN = isonicotinic acid), has been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction. Structural analysis shows that compound 1 possesses a three-dimensional framework with 4-connected threefold interpenetrated diamond (dia) topological network where the Zn(II) centers are all 4-coordinated. Moreover, the photoluminescent property of this compound is investigated in the solid state at room temperature.Graphical abstractThe first zinc(II) isonicotinic complex with threefold interpenetration of diamond topological net was synthesized and characterized.

•Presented here is a microporous formate framework.•The HCOO- was in situ generated from the decomposition of DMF.•The desolvated framework shows highly selective CO2 capture.A metal–organic framework [Mn3(HCOO)6]·DMF (1) with in situ generated formate ligand from the decomposition of N,N-dimethylformamide (DMF) solvent has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Infrared Spectroscopy (IR) and Elemental analysis (EA). Each formate ligand acts as μ3-bridge to link three octahedral Mn(II) centers to form a neutral three-dimensional (3D) framework with interesting 1D zigzag channel along the b axis, in which the DMF fill the free spaces. The desolvated samples exhibit interesting adsorption properties and show high selectivity for the adsorption of CO2 over N2 under ambient conditions.Presented here is a microporous Mn-based metal–organic framework, which exhibits high selectivity for the adsorption of CO2 over N2 under ambient conditions.

Presented here are two three-dimensional metal–organic frameworks [H2N(CH3)2]2[Cd5(bdt)3(btc)2(H2O)2]·3(H2O) (1) (H2bdt = 1,4-benzeneditetrazol-5-yl; H3btc = 1,3,5-benzenetricarboxylic acid) and [Cd5(Hbdt)2(bdt)(btc)2(H2O)2]·4H2O (2) with integrated topological nets, where the trinuclear cadmium units act as 10-connected nodes. Since both compounds are built from a dual-ligand assembly approach, the topological analyses on the networks of compounds 1 and 2 are also considered as the integration of two nets. For compound 1, its net is integrating an xbe net of Cd–bdt connectivity and kgd net of Cd–btc connectivity, while the net of compound 2 is integrating a fry net of Cd–bdt connectivity and kgd net of Cd–btc connectivity. Furthermore, the luminescence properties of the two compounds are investigated in the solid state at room temperature.

The cooperative assembly of mixed 2-aminoisonicotinate and adeninate ligands with Zn2+ centers generates a porous tetrahedral framework material with rich amino groups in the pores, which shows high CO2 uptake at 0.1 bar, high enthalpy of CO2 adsorption (40 kJ mol−1) and excellent adsorption selectivity of CO2 over N2 under ambient conditions.

•Synthesis of two new three-dimensional metal-organic frameworks.•The metal organic framework of 1 with unusual 4-connected pts topology.•Zn-Li heterometallic organic framework 2 with (4, 4, 8)-connected network topology.Two new three-dimensional metal–organic frameworks, [H2N(CH3)2]2[Zn(btec)]·DMF (1, H4btec = 1,2,4,5-benzenetetracarboxylate acid) and [H2N(CH3)2][ZnLi(btec)]·DMF (2), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction. Compound 1 based on μ4-btec features an anionic homometallic framework with 4-connected pts topology. Compound 2 is a heterometallic organic framework with rare (4, 4, 8)-connected network topology, which can be considered as constitute of a Li-btec (pts) net and a Zn-btec net. Moreover, the luminescent properties of two compounds are investigated in the solid state at room temperature.Two new 3D homometallic and heterometallic metal–organic frameworks were synthesized and structurally characterized as a pts network and a rare (4, 4, 8)-connected network.

A new three-dimensional (3D) metal–organic framework (MOF) {Zn5(μ3-OH)2(obb)4[(CH3)2NH]2}·2DMF (1; H2obb = 4,4′-oxybisbenzoic acid; DMF = N,N′-dimethyl formamide) with unusual Zn5(μ3-OH)2(COO−)8 secondary building units (SBUs) has been solvothermally synthesized and structurally characterized by the aid of single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Elemental analysis (EA) and Infrared Spectroscopy (IR). The unprecedented pentanuclear Zn5(μ3-OH)2(COO−)8 SBU was formed by two trimeric Zn3(μ3-OH)(COO−)6 SBUs, which can be simplified as 4-connected node. Correspondingly, compound 1 exhibits dia structural topology.Presented here is a new 4-connected dia zinc–organic framework with unusual Zn5(μ3-OH)2(COO−)8 SBUs.Highlights► A new zinc–organic framework with unusual pentanuclear Zn5(μ3-OH)2(COO−)8 SBUs ► Pentanuclear Zn5(μ3-OH)2(COO−)8 SBU formed by two trimeric Zn3(μ3-OH)(COO−)6 SBUs by sharing the Zn2 atom ► The observation of interesting double helix chain and 4-connected dia topology based on Zn5(μ3-OH)2(COO−)8 SBUs.

A new 3D metal-organic framework [Cu(en)(ntd)](e-urea)(H2O) (1; en = 1,2-ethylenediamine, ntd = 1,4-Naphthalenedicarboxylic acid, e-urea = 2-imidazolidinone hemihydrate), has been synthesized by urothermal method. Structural analysis shows that compound 1 possesses unprecedented (3,4)-connected tfi topology. 2-imidazolidinone, one of the urea derivatives, plays multiple roles in the self-assembly of compound 1.A new 3D metal-organic framework with in situ generated ligand was synthesized urothermally and structurally characterized as a (3,4)-connected tfi network.Highlights► Urothermal synthesis of a metal organic framework/ ► The metal organic framework with unusual (3,4)-connected tfi topology/ ► In situ ligand synthesis from 2-imidazolidinone to 1,2-ethylenediamine.

Presented here are the hydrothermal synthesis, single crystal XRD characterization and physical property of a polymeric lead(II) compound, [Pb3Cl3(OH)(succinate)]n (1). In the structure of 1, the succinate ligands bridge the trinuclear incomplete cubane-like Pb3O3Cl clusters to form a non-interpenetrating three-dimensional framework with lvt (4284) topology. Single helices with the same ratio of different orientation are found in this unusual network.Presented here are the hydrothermal synthesis, structure and physical property of a polymeric lead(II) compound, [Pb3Cl3(OH)(succinate)]n (1), which is formed from the trinuclear incomplete cubane-like Pb3O3Cl clusters and shows a non-interpenetrating three-dimensional framework with lvt (4284) topology.Research Highlights► This work reports a non-interpenetrating helical 4-connected lvt topological network, [Pb3Cl3(OH)(succinate)]n (1). ► It contains trinuclear incomplete cubane-like Pb3O3Cl clusters and succinate ligands as planar 4-coordination nodes. ► Single helices with the same ratio of different orientation are found in this unusual network.

Three tetrahedral tetrazolate frameworks (TTFs) with SOD, srs and ctn topologies (TTF-4, -5 and -6) are obtained by using the anion and solvent as structure-directing agents. The resulting SOD-type TTF-4 shows high chemical stability as well as high CO2 uptake capacity.

A new pillared-layer metal–organic framework [Zn2(NH2-BTB)(2-nim)] (1) was successfully synthesized based on mixed ligands, where binuclear [Zn2(CO2)3]+ cluster-based cationic layers [Zn2(NH2-BTB)]+ (NH2-H3BTB = 1,3,5-(three-benzoic acid)aniline) are connected by 2-nitroimidazoles. Compound 1 shows high uptake and good adsorption selectivities for C3/C1 and C2/C1. Particularly, the C2H2 uptake capacity of 1 is up to 152 cm3 g−1 at 273 K and the selectivity for C3H8/CH4 is over 85 at room temperature.