Fei Wang

Luminescent MTN-type cluster-organic framework with 2.6 nm cages.

From a basic tetrahedral Cu(4)I(4) cluster, a new MTN-type cluster-organic framework (COZ-1) containing giant 6(4)5(12) and 5(12) cages was successfully constructed. The 6(4)5(12) cage has an inner diameter of 2.6 nm and a large pore volume of 9.2 nm(3); these tetrahedral Cu(4)I(4) clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.

Copper‐Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF3‐Containing Alkyl Azides

A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3 -containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3 -containing amine derivatives.

Doping copper into ZIF-67 for enhancing gas uptake capacity and visible-light-driven photocatalytic degradation of organic dye

A doping strategy was successfully applied to tune the gas sorption and photocatalytic properties of a microporous material ZIF-67. The Cu-doped phase integrated both structural features and functions of ZIF-67 showed high gas uptake capacity and highly efficient visible-light-driven photocatalytic property on the degradation of methyl orange.

N-Tosyl-S-difluoromethyl-S-phenylsulfoximine: A New Difluoromethylation Reagent for S-, N-, and C-Nucleophiles

The first alpha-difluoromethyl sulfoximine compound, 2, was successfully prepared by using the copper(II)-catalyzed nitrene transfer reaction. Compound 2 was found to be a novel and efficient difluoromethylation reagent for transferring the CF(2)H group to S-, N-, and C-nucleophiles. Deuterium-labeling experiments suggest that a difluorocarbene mechanism is involved in the current difluoromethylation reactions.

Interrupted zeolite LTA and ATN-type boron imidazolate frameworks.

Zeolite A (LTA) is of much interest in zeolite family because of its large-scale industrial applications. Making Zeolite A (a typical 4-connected tetrahedral framework material) with a lower connectivity (3-connected) might lead to new open architecture with expanded ring size and enhanced functionality. The first interrupted Zeolite A with 3-connected network has been experimentally realized here by a boron imidazolate (im) framework material (BIF-20) with 3-coordinate BH(mim)(3)(-) building units. Additionally, a new strategy toward the construction of functional microporous metal-organic frameworks with interrupted zeolite-type topologies is presented by both 3-connected boron imidazolate frameworks (BIF-20 and BIF-21). BIF-20 has an unusual tetrahedral framework with both debonded α and β cages, and exhibits high H(2) uptake capacity.

Alkaline earth metal ion doped Zn(II)-terephthalates

Alkaline earth metal ion doped Zn(II)-terephthalates, [Zn2Mg(PBDC)3(DMA)2]n (1), [ZnCa(PBDC)2(DMA)2]n (2), [ZnSr(PBDC)2(DMA)2]n (3) and [Zn2Ba(PBDC)3(μ2-O1w)2(DMF)]n·n(DMF) (4) (H2PBDC = terephthalic acid, DMA = N,N′-dimethylacetamide, DMF = N,N′-dimethylformamide), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra, and thermal analyses. Different secondary building subunits, [Zn2Mg(μ2-COO)3] for 1, [ZnCa(μ2-COO)3] for 2, [ZnSr(μ2-COO)3] for 3, and [Zn2Ba(μ2-COO)4(μ2-O1w)2] for 4, are realized by the introduction of different alkaline earth ions. Compound 1 is a two-dimensional (2D) layer structure with 6-connected hxl topology. Compounds 2 and 3 are isostructural and exhibit a three-dimensional (3D) framework with (3,5)-connected {4.62}{4.66.83} topology owing to their similar secondary building subunits. Compound 4 is a three-dimensional (3D) opened framework with the channels occupied by the disordered lattice DMF molecules and can be simplified into a (3,8)-connected {42.6}2{44.614.78.82} topology. Moreover, the solid-state fluorescence of compounds 1–4 have also been investigated at room temperature.

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Direct methods for stereoselective functionalization of sp3-hybridized carbon–hydrogen [C(sp3)–H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.

Asymmetric transfer hydrogenation of ketones and imines with novel water-soluble chiral diamine as ligand in neat water

A novel water-soluble rhodium(III)catalyst prepared from o,o′-aminated N-tosyl-1,2-diphenylethylenediamine(S,S)-3 and [Cp*RhCl2]2, which was efficient for the asymmetric transfer hydrogenation of ketones and imines in neat water with high reactivity and excellent enantioselectivity, has been developed.

Charge Matching on Designing Neutral Cadmium–Lanthanide–Organic Open Frameworks for Luminescence Sensing

Through careful consideration of charge matching, a simple replacement of metal ion from Cd(2+) to Ln(3+) in a building unit successfully transforms an anionic microporous framework into a series of isostructural porous neutral heterometallic frameworks [Cd(3)Ln(2)(btc)(4)(H(2)O)(6)(dmf)(4)]·x(solvent) (1; Ln=Tb, Eu, Nd, Gd, Sm, dmf=N,N-dimethylformamide) by employing five different lanthanide ions. 1-Tb and 1-Eu exhibit interesting photoluminescent properties, and remarkably, 1-Tb can act as a luminescent sensor to identify organic solvents and metal ions.

Induction in urothermal synthesis of chiral porous materials from achiral precursors.

Special asymmetric crystallization of porous framework materials from achiral precursors under urothermal conditions is successfully achieved by using an enantiopure liquid as a co-solvent and chirality induction agent, which provides a new strategy for the synthesis of homochiral porous materials containing only achiral building blocks.