A 12-connected metal-organic framework constructed from an unprecedented cyclic dodecanuclear copper cluster

A 12-connected metal-organic framework based on an unprecedented cyclic Cu(12) cluster with a large internal cavity has been prepared, and its cation exchange property was determined.     

An unprecedented twofold interpenetrating (3,4)-connected 3-D metal-organic framework

An unprecedented twofold interpenetrating (3,4)-connected topology of the Cu(3)L(4)-type metal-organic framework was prepared using N,N',N'-tris(4-pyridinyl)-1,3,5-benzenetricarboxamide (L) as a trigonal three-connection node and the copper(ii) ion as a square planar four-connection node, where the framework contains remarkably large 1-D solvent channels.     

A 3D canted antiferromagnetic porous metal-organic framework with anatase topology through assembly of an analogue of polyoxometalate

The unique porous metal-organic framework {KCo3(C6H4O7)(C6H5O7)(H2O)2.8H2O}8 (1), which exhibits an unprecedented infinite 3D (3,6)-connected decorated anatase net, has been obtained by hydrothermal reaction. Upon dehydration, the compound retains crystallinity and exhibits a type I N2 sorption isotherm, characteristic of a microporous solid with apparent Langmuir surface area 939 m2/g and pore volume 0.31 cm3/g. Magnetic measurements for both 1 and dehydrated 1 show the spin-canted antiferromagnetic state below 5 K and a magnetic hysteresis loop at 2 K. Thus, dehydrated 1 represents the first metal-organic framework for which microporosity and a spin-canted antiferromagnetic state coexist, which demonstrates that the self-assembly of organo-polymetal clusters and metal ions can provide a potential route to magnetic porous metal-organic frameworks.     

Microporous 3-D chiral metal-organic framework with a quartzlike topology based on an achiral building unit

A zinc coordination polymer, Zn(IN)₂ · 2H₂O (1) (HIN = isonicotinic acid), has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single crystal X-ray diffraction. This compound crystallizes in the chiral space group P6₂ with a = 15.512(3), b = 15.512(3), c = 6.262(2) Å, V = 1304.9(5) ų, and Z = 3. The O and N atoms of the IN ligand are coordinated to a Zn^II ion, locking the asymmetry of the IN ligand and transferring this asymmetry throughout the crystal structure to “direct” the formation of a chiral network. The structure of 1 is characteristic of a 3-D quartz-like framework, which contains hetero-chiral helical channels (pseudo-trigonal and hexagon channels) alternately along the c-axis. Compound 1 exhibits high stability and intense fluorescent emission at room temperature.     

One-dimensional metal-organic framework with unprecedented heptanuclear copper units

The reaction of copper(II) sulfate, copper(II) chloride, 3,5-diacetylamino-1,2,4-triazole, and 3-acetylamino-5-amino-1,2,4-triazole in water yields green, plate-shaped crystals of [[{Cu3(mu3-OH(1/2))L(H2O)2Cl}2{mu-Cu(H2O)2Cl2}].12H2O]n (1), where L is a new triazole-derived macrocyclic ligand. The structure of 1 consists of heptanuclear (H)OCuII(3)-CuII-CuII(3)O(H) entities linked in pairs through symmetric mu3-O...H...O-mu3 hydrogen bonds to form a double-stranded one-dimensional network. A significant overall antiferromagnetic behavior has been observed for 1.     

Homochiral 3D lanthanide coordination networks with an unprecedented 4(9)6(6) topology

Homochiral 3D metal-organic open frameworks based on enantiopure atropisomeric dicarboxylic acid bridging ligands and dilanthanide secondary building units exhibit an unprecedented 4(9)6(6) topology, and possess ethoxy-protected BINOL functionalities that are pointing toward the open channels.     

A lanthanide-based metal-organic framework with a dynamic porous property

Hydrothermal reaction of La(NO(3))(3), NaHCO(3) and H(3)L (H(3)L = pyrazole-3,5-dicarboxylic acid) gives a 3D metal-organic framework with a dynamic porous property.     

A three-dimensional porous metal-organic framework with the rutile topology constructed from triangular and distorted octahedral building blocks

The solvothermal reaction of zinc acetate dihydrate with 1,3,5-benzenetricarboxylic acid yields a three-dimensional porous metal-organic framework constructed from triangular and distorted octahedral building blocks, the framework of which can be described as a decorated rutile net.     

A non-interpenetrated porous metal-organic framework with high gas-uptake capacity

A novel microporous polyhedral framework [Zn(6)(btb)(4)(4,4'-bipy)(3)(dmf)(55)(H(2)O)(32)] with high surface area has been designed and synthesized, which shows high multigas-uptake capacity via supercritical carbon dioxide (SCD) activation.     

Homochiral laminar europium metal-organic framework with unprecedented giant dielectric anisotropy

Hydrothermal (deuteratothermal) reaction of L-ethyl lactate (Lig-Et) with Eu(ClO(4))(3)6 H(2)O gives colorless block crystals of [Eu(Lig)(2)(X(2)O)(2)][ClO(4)] (1, X=H; 2, X=D) both of which possess a two-dimensional laminar homochiral framework. Single-crystal dielectric measurements reveal that 1 and 2 display a giant dielectric anisotropy approximately exceeding 100 and large isotopic effect with about 54 % enhancement along the a axis. Their ferroelectric features further confirm this respect. Crystal parameters: 1, C(6)H(14)ClO(12)Eu, M(r)=465.58, monoclinic, C(2), a=8.6786(6), b=8.3965(6), c=10.2153(7) A, beta=92.040(1) degrees , V=743.92(9) A(3), Z=2, rho(calcd)=2.079 Mg m(-3), R(1)=0.0508, wR(2)=0.1239, mu=4.448 mm(-1), S=1.043; Flack=0.04(5). 2: C(6)H(10)D(4)ClO(12)Eu, M(r)=469.61, monoclinic, C(2), a=8.689(2), b=8.410(2), c=10.224(3) A, beta=92.057(4) degrees , V=746.7(3) A(3), Z=2, rho(calcd)=2.089 Mg m(-3), R(1)=0.0465, wR(2)=0.1150, mu=4.432 mm(-1), S=1.058; Flack=0.02(5).     

3D porous metal-organic framework exhibiting selective adsorption of water over organic solvents

A 3D porous metal-organic framework (MOF) with 1D open channels has been constructed hydrothermally using Zn(II) and a rigid planar ligand IDC(3)- (imidazole-4,5-dicarboxylate). This MOF can adsorb water selectively over organic solvents and can be regenerated and reused. It also represents a rare example of a MOF with open channels that form/collapse reversibly upon hydration/dehydration.     

A novel chiral porous metal-organic framework: asymmetric ring opening reaction of epoxide with amine in the chiral open space

A novel chiral metal-organic framework, [Cu(2)(5,5'-BDA)(2)] was synthesized by treating chiral 2,2'-dihydroxy-1,1'-binaphthalene-5,5'-dicarboxylic acid (5,5'-H(2)BDA) with a Cu(II) ion, in which the asymmetric ring opening reaction of an epoxide with amine proceeds efficiently under solvent-free conditions.     

A rod packing microporous metal-organic framework: unprecedented ukv topology, high sorption selectivity and affinity for CO2

An unprecedented ukv topological framework, based on a rod-like cadium-carboxylate chain, exhibits high CO(2) sorption heat and sorption selectivities of CO(2) over N(2) and CH(4).     

The first metal-organic framework containing an unprecedented in situ-generated C-substituted hexamethylenetetramine ligand

The first metal-organic framework containing an unprecedented in situ-generated C-substituted hexamethylenetetramine ligand has been successfully prepared by the reaction of silver nitrate, 4-formylbenzoic acid and hexamethylenetetramine under traditional solution conditions, which holds the unusual (3,4)-connected topological network.     

A chiral metal-organic framework for sequential asymmetric catalysis

A chiral metal-organic framework (MOF) of the lcy topology was constructed from the Mn-Salen derived dicarboxylic acid and the [Zn(4)(μ(4)-O)(O(2)CR)(6)] secondary building unit, and used in highly regio- and stereo-selective sequential alkene epoxidation/epoxide ring-opening reactions.     

A chiral porous metal-organic framework for highly sensitive and enantioselective fluorescence sensing of amino alcohols

A highly porous and fluorescent metal-organic framework (MOF), 1, was built from a chiral tetracarboxylate bridging ligand derived from 1,1'-bi-2-naphthol (BINOL) and a cadmium carboxylate infinite-chain secondary building unit. The fluorescence of 1 can be effectively quenched by amino alcohols via H-bonding with the binaphthol moieties decorating the MOF, leading to a remarkable chiral sensor for amino alcohols with greatly enhanced sensitivity and enantioselectivity over BINOL-based homogeneous systems. The higher detection sensitivity of 1 is due to a preconcentration effect by which the analytes are absorbed and concentrated inside the MOF channels, whereas the higher enantioselectivity of 1 is believed to result from enhanced chiral discrimination owing to the cavity confinement effect and the conformational rigidity of the BINOL groups in the framework. 1 was quenched by four chiral amino alcohols with unprecedentedly high Stern-Volmer constants of 490-31200 M(-1) and enantioselectivity ratios of 1.17-3.12.     

A novel low density metal-organic framework with pcu topology by dendritic ligand

A novel low density two-fold interpenetrated MOF-5 analogue with pcu topology, JUC-100, was designed and prepared successfully. It can be regarded as MOF-5 in which half of the Zn(4)O(CO(2))(6) units are replaced by organic 1,3,5-triphenylbenzene segments. JUC-100 exhibits H(2) uptake ability comparable to interpenetrated MOF-5, but relatively low initial isosteric heat of adsorption.     

Three-dimensional metal-organic framework with (3,4)-connected net, synthesized from an ionic liquid medium

A new 3D metal-organic framework with a (3,4)-connected network topology is synthesized from an ionic liquid medium; its highly symmetrical structure comprises doubly interpenetrating nets with the cubic-C3N4 topology.