Multi-component synthesis of 2-amino-6-(alkyllthio)pyridine-3,5-dicarbonitriles using Zn(II) and Cd(II) metal-organic frameworks (MOFs) under solvent-free conditions.

Multi-component synthesis 2-amino-3,5-dicarbonitrile-6-thio-pyridines has been developed by using the reaction of aldehydes, malononitrile, and thiophenols in the presence of a Zn (II) or a Cd(II) metal-organic framework (MOF) as the heterogeneous catalyst. This protocol tolerates different functional groups on the substrates and does not require the use of any organic solvent. Moreover, the Zn(II) and Cd (II) MOF catalysts can be recovered and reused for a number of runs without loss of activity.

Second-order nonlinear optical activity induced by ordered dipolar chromophores confined in the pores of an anionic metal-organic framework.

Frequency doubling: A strategy for incorporating dipolar organic chromophores into the one-dimensional channels of an anionic metal-organic framework (MOF) has been developed to generate highly active nonlinear optical materials (see picture). The resulting MOF material shows a second-harmonic generation intensity of 18.3 versus α quartz.

Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions.

Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve such separations and to replace current technologies, which use aqueous solvents to chemically absorb carbon dioxide. Here we show that a metal-organic frameworks (UTSA-16) displays high uptake (160 cm(3) cm(-3)) of CO(2) at ambient conditions, making it a potentially useful adsorbent material for post-combustion carbon dioxide capture and biogas stream purification.

Three novel isomeric zinc metal-organic frameworks from a tetracarboxylate linker.

Three porous supramolecular isomers (IZE-1, IZE-2, and IZE-3) with the same framework component [Zn(2)(EBTC)(H(2)O)(2)] (EBTC = 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate) were successfully constructed by finely tuning the reaction condition. Although both IZE-1 and IZE-2 are constructed from the linear EBTC subunits and one kind of regular [Zn(2)(CO(2))(4)] paddlewheels, their frameworks exhibit two different (3,4)-c net of fof (sqc1575) and sqc1572, respectively, resulting in cavities with different size and shape. However, as for isomer IZE-3, the EBTC ligands are bent and one-half of the [Zn(2)(CO(2))(4)] paddlewheels are distorted, leading to a novel (3,4,4)-c hyx net with point symbol (6.

Porous metalloporphyrinic frameworks constructed from metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin for highly efficient and selective catalytic oxidation of alkylbenzenes.

We incorporate metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-H(8)OCPP), for the first time, into porous metal-organic frameworks. The self-assembled porous metalloporphyrinic frameworks [Mn(5)Cl(2)(MnCl-OCPP)(DMF)(4)(H(2)O)(4)]·2DMF·8CH(3)COOH·14H(2)O (ZJU-18; ZJU = Zhejiang University), [Mn(5)Cl(2)(Ni-OCPP)(H(2)O)(8)]·7DMF·6CH(3)COOH·11H(2)O (ZJU-19), and [Cd(5)Cl(2)(MnCl-OCPP)(H(2)O)(6)]·13DMF·2CH(3)COOH·9H(2)O (ZJU-20) are isostructural as revealed by their single X-ray crystal structures. The metalloporphyrin octacarboxylates (M-OCPP) (M = Mn(III)Cl for ZJU-18 and ZJU-20, M = Ni(II) for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of about 11.

A luminescent nanoscale metal-organic framework with controllable morphologies for spore detection.

A nanoscale MOF material NMOF 1 with controllable morphologies is realized whose morphology control has been simulated based on the BFDH method. The targeted NMOF 1 exhibits highly sensitive, selective and instant "turn-on" sensing of bacterial endospores.

A robust doubly interpenetrated metal-organic framework constructed from a novel aromatic tricarboxylate for highly selective separation of small hydrocarbons.

A microporous metal-organic framework, for the first time, has been developed for highly selective separation of industrially important C(1), C(2) and C(3) hydrocarbons at room temperature.

Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules.

Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C(2)H(2)/C(2)H(4) separation.

Triple framework interpenetration and immobilization of open metal sites within a microporous mixed metal-organic framework for highly selective gas adsorption.

A three-dimensional triply interpenetrated mixed metal-organic framework, Zn(2)(BBA)(2)(CuPyen)·G(x) (M'MOF-20; BBA = biphenyl-4,4'-dicarboxylate; G = guest solvent molecules), of primitive cubic net was obtained through the solvothermal reaction of Zn(NO(3))(2), biphenyl-4,4'-dicarboxylic acid, and the salen precursor Cu(PyenH(2))(NO(3))(2) by a metallo-ligand approach. The triple framework interpenetration has stabilized the framework in which the activated M'MOF-20a displays type-I N(2) gas sorption behavior with a Langmuir surface area of 62 m(2) g(-1). The narrow pores of about 3.

A luminescent mixed-lanthanide metal-organic framework thermometer.

A luminescent mixed lanthanide metal-organic framework approach has been realized to explore luminescent thermometers. The targeted self-referencing luminescent thermometer Eu(0.0069)Tb(0.

High separation capacity and selectivity of C2 hydrocarbons over methane within a microporous metal-organic framework at room temperature.

A separation story! A microporous metal-organic framework (UTSA-34) of non-interpenetrated binodal (4,6)-connected ybh network with interconnected cages of about 12.8 Å has been realised to exhibit highly selective separation of C(2) hydrocarbons from methane with a separation capacity of 3.0 mol  kg(-1) and selectivity of 35 at room temperature (see figure).

A microporous metal-organic framework for highly selective separation of acetylene, ethylene, and ethane from methane at room temperature.

A novel three-dimensional microporous metal-organic framework Zn(4)L(DMA)(4) (UTSA-33, H(8) L=1,2,4,5-tetra(5-isophthalic acid)benzene, DMA=N,N'-dimethylacetamide) with small pores of about 4.8 to 6.5 Å was synthesized and structurally characterized as a non-interpenetrated (4,8)-connected network with the flu topology (Schläfli symbol: (4(12)6(12)8(4))(4(6))(2)).

Hydrogen-bonding 2D metal-organic solids as highly robust and efficient heterogeneous green catalysts for Biginelli reaction.

Two new Zn(II) and Cd(II) MOFs have been synthesized. These MOFs have been applied as heterogeneous catalysts for the green synthesis of a variety of dihydropyrimidinone derivatives through the Biginelli reaction and the desired products were obtained in high yields with short reaction time under mild solvent- free conditions. Moreover, the MOF catalysts may be readily recovered after the reaction and reused for many cycles.

A Zn4O-containing doubly interpenetrated porous metal-organic framework for photocatalytic decomposition of methyl orange.

A doubly interpenetrated semiconducting MOF Zn(4)O(2,6-NDC)(3)(DMF)(1.5)(H(2)O)(0.5)·4DMF·7.

Functional mixed metal-organic frameworks with metalloligands.

Immobilization of functional sites within metal-organic frameworks (MOFs) is very important for their ability to recognize small molecules and thus for their functional properties. The metalloligand approach has enabled us to rationally immobilize a variety of different functional sites such as open metal sites, catalytic active metal sites, photoactive metal sites, chiral pore environments, and pores of tunable sizes and curvatures into mixed metal-organic frameworks (M'MOFs). In this Minireview, we highlight some important functional M'MOFs with metalloligands for gas storage and separation, enantioselective separation, heterogeneous asymmetric catalysis, sensing, and as photoactive and nanoscale drug delivery and biomedical imaging materials.

A microporous hydrogen-bonded organic framework for highly selective C2H2/C2H4 separation at ambient temperature.

The first microporous hydrogen-bonded organic framework with permanent porosity and exhibiting extraordinarily highly selective adsorptive separation of C(2)H(2) and C(2)H(4) at ambient temperature has been established.

A new approach to construct a doubly interpenetrated microporous metal-organic framework of primitive cubic net for highly selective sorption of small hydrocarbon molecules.

A new approach has been realized to construct a three-dimensional doubly interpenetrated cubic metal-organic framework Zn(2)(PBA)(2)(BDC)·(DMF)(3)(H(2)O)(4) (UTSA-36, HPBA=4-(4-pyridyl) benzoic acid, H(2)BDC=1,4-benzenedicarboxylic acid) through the self-assembly of the pyridylcarboxylate linker 4-(4-pyridyl) benzoate and bicarboxylate linker 1,4-benzenedicarxylate with paddle-wheel [Zn(2)(COO)(4)]. The activated UTSA-36a exhibits highly selective gas sorption of C(2)H(6), C(2)H(4) and C(2)H(2) over CH(4) with the Henry law's selectivities of 11 to 25 in the temperature range of 273 to 296 K attributed to the unique 3D intersected pore structure of about 3.1 to 4.

A robust near infrared luminescent ytterbium metal-organic framework for sensing of small molecules.

The first near-infrared luminescent ytterbium metal-organic framework has been realized for the highly selective and sensitive sensing of small molecules.

Three-dimensional pillar-layered copper(II) metal-organic framework with immobilized functional OH groups on pore surfaces for highly selective CO2/CH4 and C2H2/CH4 gas sorption at room temperature.

A new three-dimensional microporous metal-organic framework Cu(BDC-OH)(4,4'-bipy)·G(x) (UTSA-15; H(2)BDC-OH = 2-hydroxy-benzenedicarboxylic acid, 4,4'-bipy =4,4'-bipyridine, G = guest molecules) with functional -OH groups on the pore surfaces was solvothermally synthesized and structurally characterized. UTSA-15 features a three-dimensional structure having 2D intercrossed channels of about 4.1 × 7.

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene.

Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C(2)H(2)/C(2)H(4) have not been realized to date.

A luminescent nanoscale metal-organic framework for sensing of nitroaromatic explosives.

The first nanoscale luminescent metal-organic framework has been realized for the straightforward and highly sensitive sensing of nitroaromatic explosives in enthanol solution.

A rod packing microporous metal-organic framework with open metal sites for selective guest sorption and sensing of nitrobenzene.

A microporous MOF [Zn(4)(OH)(2)(1,2,4-BTC)(2)] (1,2,4-BTC = Benzene-1,2,4-tricarboxylate) with two immobilized open metal Zn(2+) sites was obtained by solvothermal reaction, which exhibits highly selective guest sorption and sensing of nitrobenzene.

A robust highly interpenetrated metal-organic framework constructed from pentanuclear clusters for selective sorption of gas molecules.

A three-dimensional microporous metal-organic framework, Zn(5)(BTA)(6)(TDA)(2)·15DMF·8H(2)O (1; HBTA = 1,2,3-benzenetriazole; H(2)TDA = thiophene-2,5-dicarboxylic acid), comprising pentanuclear [Zn(5)] cluster units, was obtained through an one-pot solvothermal reaction of Zn(NO(3))(2), 1,2,3-benzenetriazole, and thiophene-2,5-dicarboxylate. The activated 1 displays type-I N(2) gas sorption behavior with a Langmuir surface area of 607 m(2) g(-1) and exhibits interesting selective gas adsorption for C(2)H(2)/CH(4) and CO(2)/CH(4).