Search

Metal-organic cages, a class of supramolecular containers constructed by the self-assembly of metal ions and organic ligands, show great promise as catalytic agents. In this work, we designed and synthesized a series of rhombic dodecahedral Ni-Cu heterometal imidazolate cages (Ni8Cu6L24) that can act as highly active photo-Fenton-like catalysts. These cages possess a high ability to generate hydroxyl radicals (•OH) under visible light in the presence of H2O2, which can rapidly degrade organic pollutants (e.g., rhodamine B, methylene blue, and methyl orange) into CO2 and H2O. Besides, they are robust catalysts, with high catalytic activity and reusability under conditions in high H2O2 concentration, providing potentially advanced materials for degrading persistent organic pollutants.

Water oxidation to molecular oxygen is indispensable but a challenge for splitting H2O. In this work, a series of Co-based metal-organic cages (MOCs) for photoinduced water oxidation were prepared. MOC-1 with both bis(μ-oxo) bridged dicobalt and Co-O (O from H2O) displays catalytic activity with an initial oxygen evolution rate of 80.4 mmol/g/h and a TOF of 7.49 × 10-3 s-1 in 10 min. In contrast, MOC-2 containing only Co-O (O from H2O) in the structure results in a lower oxygen evolution rate (40.8 mmol/g/h, 4.78 × 10-3 s-1), while the amount of oxygen evolved from the solution of MOC-4 without both active sites is undetectable. Isotope experiments with or without H218O as the reactant successfully demonstrate that the molecular oxygen was produced from water oxidation. Photophysical and electrochemical studies reveal that photoinduced water oxidation initializes via electron transfer from the excited [Ru(bpy)3]2+* to Na2S2O8, and then, the cobalt active sites further donate electrons to the oxidized [Ru(bpy)3]3+ to drive water oxidation. This proof-of-concept study indicates that MOCs can work as potential efficient catalysts for photoinduced water oxidation.

As a creation platform for multifunctional materials, crystalline metal–organic frameworks (MOFs) can integrate different chromophores through reticular chemistry to adjust their spatial arrangement and intermolecular interaction, in turn achieving the purpose of improving the nature of optoelectronic properties. Herein, a stepwise reticular synthesis approach is successfully used to construct a multicomponent MOF, in which the well-known bis-terpyridyl ruthenium chromophore is orderly arranged into the skeleton of the material. Remarkably, this method promotes the excited state lifetime of the bis-terpyridyl ruthenium core, by two orders of magnitude (from 0.39 to 22.09 ns), to the extent that it can produce singlet oxygen under visible light irradiation at room temperature. Meanwhile, the obtained multicomponent MOF has been established to have considerable porosity for exposure of substrates to the catalytic sites, rendering it suitable for heterogeneous photocatalysis, including as a photooxidation detoxifier for sulfur mustard simulant. Moreover, DFT and TDDFT calculations reveal that the synergistic charge transfer among different components in the MOF may play a crucial role in improving the excited state properties of the bis-terpyridyl ruthenium motif.

Polynuclear silver clusters are described that unexpectedly transform from cyclic trinuclear complexes (CTCs) upon reacting with σ-donating phenylacetylene, featuring a noria-like conformation. The introduction of foreign copper ions leads to isomorphic bimetallic Ag/Cu clusters, with a boost in the photoluminescence quantum yield relative to the original silver clusters.

Two mixed-valence CuII/CuI and two heterometallic CuII/AgI metallocycles have been synthesized by the assembly of designed metalloligands and CuI/AgI ions, respectively. The CuII/CuI metallocycle can catalyze the oxidation of alcohols to aldehydes mediated by a co-catalyst, TEMPO (2,2,6,6-tetramethylpiperdine-1-oxyl), with ambient air as an oxidant, while the CuII/AgI metallocycle has no catalytic effect.

Charge separation plays a crucial role in regulating photochemical properties and therefore warrants consideration in designing photocatalysts. Metal-organic frameworks (MOFs) are emerging as promising candidates for heterogeneous photocatalysis due to their structural designability and tunability of photon absorption. Herein, we report the design of a pyrazole-benzothiadiazole-pyrazole organic molecule bearing a donor-acceptor-donor conjugated π-system for fast charge separation. Further attempts to integrate such a photosensitizer into MOFs afford a more effective heterogeneous photocatalyst (JNU-204). Under visible-light irradiation, three aerobic oxidation reactions involving different oxygenation pathways were achieved on JNU-204. Recycling experiments were conducted to demonstrate the stability and reusability of JNU-204 as a robust heterogeneous photocatalyst. Furthermore, we illustrate its applications in the facile synthesis of pyrrolo[2,1

Metalloenzymes are powerful biocatalysts that can catalyze particular chemical reactions with high activity, selectivity, and specificity under mild conditions. Metal-organic frameworks (MOFs) composed of metal ions or metal clusters and organic ligands with defined cavities have the potential to impart enzyme-like catalytic activity and mimic metalloenzymes. Here, a new metal-organic framework implanted with hydroxo iron(III) sites with the structural and reactivity characteristics of iron-containing lipoxygenases is reported. Similar to lipoxygenases, the hydrogen atoms and electrons of the substrate can transfer to the hydroxo iron(III) sites, showing typical proton-coupled electron transfer behavior. In the reactivity mimicking biology system, similar to alcohol oxidase, the material also catalyses the oxidation of alcohol into aldehyde by using O2 with a high yield and 100% selectivity under mild conditions, without the use of a radical cocatalyst or photoexcitation. These results provide strong evidence for the high structural fidelity of enzymatically active sites in MOF materials, verifying that MOFs provide an ideal platform for designing biomimetic heterogeneous catalysts with high conversion efficiency and product selectivity.

Metal-organic cages are potential artificial models for mimicking biological functions due to their capability of selective encapsulation for certain guest molecules. In this work, we designed and synthesized a series of rhombic dodecahedral Ni-imidazolate cages (Ni

A variety of planar organic fluorophores (R=phenyl, naphthalenyl, pyrenyl) and luminescence promotors (X=Cl, Br, I) were equipped, respectively, on the alternatively arranged vertices of cubic ZnII -imidazolate cages through orthogonal subcomponent self-assembly. It was found that supramolecular interactions, especially weak C-H⋅⋅⋅X interactions, play a key role in activating an efficient radiative pathway, coupled with reduced nonradiative decay rate through metal coordination, therefore significantly boosting the emission quantum yields of the system. This finding provides a strategy that utilizes molecular geometry and supramolecular interactions to modulate the emission efficiency of luminescent cage-based materials.

In this work, Zn2+ and Cu2+ ions are doped into a Mn2+ based frail MOF (STU-2) to form heterometallic MOFs. These metal doped MOFs show a good stability and heterogeneous catalytic activity for the cyanosilylation reactions of aromatic aldehydes. The catalysts can be reused at least for three cycles.

A pair of enantiomers of three-dimensional (3D) chiral coordination polymers (CCPs) were successfully constructed by using achiral components 4,2':6',4''-terpyridyl precursors and Cu2+ through spontaneous resolution (1 a). By utilising feeding controlled chiral-templated induction and chiral auxiliary behaviour of optically pure camphor sulfonate (CSA), the enantioenriched (1 b-P and 1 b-M) and CSA captured (1 c-P and 1 c-M) CCPs were successfully synthesised, respectively. The chiral information of the corresponding products was confirmed by X-ray single crystal diffraction and solid-state CD spectra. Meanwhile, the formation processes of 1 b-P and 1 b-M were monitored through solution CD spectra, UV/Vis spectra and ESI-TOF MS. Based on these results, a reasonable chiral-templated induction mechanism of forming 1 b-P and 1 b-M was proposed.

A family of gyroidal metal-organic frameworks (STUs) composited with transition metal ions and bi-imidazolate ligands (BIm) were prepared and applied as both Lewis base and acid catalysts. Benefiting from the intrinsic basicity of the ligands and the Lewis acidic sites of the open metal centres, the STUs materials show excellent catalytic activities as Lewis base for the Knoevenagel condensation reaction between various aldehydes and malononitrile, and as Lewis acid for cyanosilylation reactions. Among these STUs, STU-4 (Ni(BIm)) shows the best catalytic efficiency (conversions >99 %) in both Knoevenagel condensation and cyanosilylation reactions under mild conditions, providing thus an advanced material for both Lewis base and Lewis acid catalysis.

A series of cubic cobalt-imidazolate cages have been successfully synthesized via subcomponent self-assembly in different solvents under solvothermal conditions. The homovalent CoII and mixed-valence CoIII,II-imidazolate cages are assembled with control over the mixed solvent ratio of N,N-diethylformamide/ethanol, respectively.

Chiral coordination cages feature both chirality and defined inner space, providing advanced molecular materials. A series of chiral 20-nucleus cobalt-imidazolate cages were synthesized by self-assembly of 72 subcomponents, featuring a novel tetartoid (tetragonal pentagonal dodecahedron) structure. Spontaneous resolution of racemic tetartoidal cages (Δ and Λ) into a conglomerate of homochiral crystals are observed, while both homochiral Δ and Λ tetartoidal cages can be obtained through chiral induction of (d)- and (l)-enantiomers of menthol, respectively. The 2-methyl substituent on imidazolyl is critical to the formation of a tetartoidal cage, and the absence of such steric effect will switch the final structure to a cubic cage.

Two one-dimensional (1D) helical coordination polymers, CuBIm–Cl and CuBIm–Br (BIm = 1,2-bis((5H-imidazol-4-yl)-methylene)hydrazine), are constructed from Cu2+ ions, halides and mono-deprotonated BIm. Solid-state crystalline conversions of CuBIm–Cl and CuBIm–Br to a gyroidal metal–organic framework (MOF) STU-3 which is composed of Cu ions and Bim ligands are observed through a gas–solid reaction, where the gas is methylamine.

Light oxygenates, such as methyl lactate (MLA), methyl levulinate (MLE), methyl formate (MFO), methyl acetate (MAC), dimethoxymethane (DMM), and methoxyacetaldehyde dimethyl acetal (MADA) were synthesized from cellulose in the presence of promoted SnX2 (X = Cl−, Br−, and I−) salt catalysts in methanol. The presence of halides in SnX2-MLn (MLn is metal salt) catalysts was found crucial for methyl lactate formation from sugar. The investigation shows that ZnCl2 is an efficient promoter for SnX2 catalyst in converting cellulose to light oxygenates. Up to 52.2% of total one-pass oxygenate yield was obtained in the presence of SnCl2–ZnCl2 catalyst.

A series of neutral cubic nickel(II)-imidazolate Ni8L12X4 cages were prepared by rational choices of substituents and anions with solvothermal subcomponent self-assembly technology. Both substituents and halide anions play a critical role in the formation and stabilization of cubic cages. Changing one of the factors in the reaction will switch the final structure to a Ni14L24 rhombic dodecahedral cage. The cubic cage can transform to a large rhombic dodecahedral cage in the presence of methylamine at room temperature accompanied by a color change from purple to light yellow.

The catalytic disproportionation of glycerol was investigated over active carbon (AC) supported catalysts. Typically, 1,2-propanediol, acetic acid, and acetaldehyde were found as the major products of the reaction over catalysts Na2CO3/AC and K2CO3/AC. Other products, such as methanol, ethanol, ethylene glycol, and acetone were also formed as the minor products in the reaction. All of these compounds are defined as oxygenate products (OP). The highest OP yield of 65.3% (carbon mol) was obtained over Na2CO3/AC at 593 K.

A strategy to improve the framework porosity and hydrophobicity of the pore surface by doping metal ions (Cu(2+), Cd(2+), or Fe(2+)) into a gyroidal MOF STU-1 has been developed. It is found that the obtained heterometallic MOFs are exceptionally water stable.

A new catalytic process for p-xylene synthesis from the methylation of toluene with CH3Br was proposed. CH3Br was prepared from the catalytic bromination of natural gas (CH4), by using H2O + HBr + O2 as mediator over supported Rh catalyst. The methylation conditions were investigated using HZSM-5 or modified HZSM-5 catalyst. Under optimal reaction conditions, p-xylene selectivity is up to 93%, and p-xylene yield is more than 21% at 673 k over the Si—P modified HZSM-5 catalyst. Compared to the processes using MeOH or dimethyl carbonate (DMC) as methylation agent, this new process is very attractive in an economic standpoint since CH4 is much cheaper than MeOH and DMC. In addition, the process has other advantages, such as mild reaction conditions, simple operation, high-product yield, and so on. It is predicted that the process has good industrial potential for para-xylene production. © 2012 American Institute of Chemical Engineers AIChE J, 59: 532–540, 2013

Phenol was synthesized from the hydroxylation of bromobenzene, which was prapared by reacting benzene with bromine. In the benzene bromination reaction, HZSM-5 (Si/Al = 400/1) was found to be a stable catalyst, which catalyzed the stoichiometric reaction of benzene with bromine. More than 90% of bromobenzene selectivity was reached over HZSM-5 and the byproduct was dibromobenzenes. In the second reaction, bromobenzene reacted with a cataloreactant to form metal bromide and phenol. This is a catalytic as well as stoichiometric reaction between bromobenzene and the metal oxide. It was found that only the supported highly dispensed metal oxide was reactive to the bromobenzene hydroxylation reaction. In this investigation, 10mol%CuO/SiO2 was found to be the most active cataloreactant for bromobenzene hydroxylation reaction.

Described in this paper are the synthesis, characterization and catalytic application of H-ZSM-5 zeolites for the conversion of CH3Br into aromatics. The H-ZSM-5 zeolites were fabricated by hydrothermal crystallization using n-butylamine (BTA) as a template and characterized by XRD, SEM and NH3-TPD techniques. The effects of batch SiO2/Al2O3 ratio, alkalinity, NaCl/Al2O3 ratio, seed crystals, and crystallization time on the yield, structure/texture and catalytic performance were systematically studied. Adopting the optimum sol (SiO2/Al2O3 = 70, BTA/SiO2 = 0.2847, Na2O/SiO2 = 0.1237, H2O/SiO2 = 37.4, NaCl/Al2O3 = 60, and seed/SiO2 = 5 wt%) and under the most preferable crystallization conditions of 100 °C/24 h–170 °C/24 h, H-ZSM-5 zeolites of high crystallinity and small size (300–700 nm) were obtained. Good catalytic performance was observed over the H-ZSM-5 zeolites (aromatic yield up to 44.2%). However, unlike the modification of large commercial HZSM-5, the use of MoO3 or PbO as modifying agents for the small-size H-ZSM-5 zeolites results in a decline of catalytic performance. The relationship between the structure and the catalytic efficiency of as-synthesized H-ZSM-5 samples were investigated. It was found that with crystallinity enhancement and/or decline in crystal size, there is improvement of catalytic performance.

A Mn-based rod metal-organic framework (MOF), ROD-6, with a new lrk net is synthesized. It represents an unusual type of MOF topology containing both a 1-periodic secondary building unit (rod SBU) and a polytopic linker (here 1,3,6,8-tetrakis(p-benzoic acid)pyrene), and also exhibits high stability (up to 485 °C) and unusual CO2 uptake behaviour and selectivity despite the lack of strong interacting sites, demonstrated by the low and increasing heat of adsorption.

A new reaction system was designed to economically convert glucose to lactic acid environment-friendly. Hydrophobic ionic liquids were chosen as solvent that can promote the decomposition reaction of glucose, and the catalytic performance of the solid bases was evaluated. Both the reaction temperature and time can affect the yield of lactic acid. A high yield (97%) of lactic acid was achieved under the optimal reaction condition. The 1H NMR spectra and HPLC-MS were used to identify the formation of the lactic acid and variations of ionic liquid. It is found that ionic-liquids have a unique solvent effect for glucose and bases. Water can be used as solvent to extract calcium lactate. This shows a great potential of hydrophobic ionic liquids in the solid bases catalyzed reaction that is limited by the weak solubility of solid bases in organic and water solution.

The catalytic conversion of CH 3 Br to aromatics was investigated over PbO-modified HZSM-5. The effects of PbO loading, SiO 2 /Al 2 O 3 molar ratio of HZSM-5, and calcination conditions of catalyst on catalytic performance were studied. It was found that the most suitable PbO loading and SiO 2 /Al 2 O 3 ratio are 5 wt% and 70, respectively. The 5 wt% PbO/HZSM-5 calcined at 450 °C for 8 h performs the best. Also, PbO is superior to the other metal oxides selected to modify HZSM-5, and HZSM-5 is better than SiO 2 , Al 2 O 3 or ZrO 2 as support. The characterization results indicate that (i) the PbO species is highly dispersed on the HZSM-5 support, (ii) the role of PbO is to promote hydrocarbon aromatization, and (iii) the acid sites of HZSM-5 are indispensable for CH 3 Br conversion into aromatics. We found that the deactivation of catalyst is due to pore blocking by carbonaceous deposits. The overall results demonstrate that the method is efficient for the conversion of CH 4 to aromatics.

Trans-1,2-cyclohexanediol was synthesized from the oxidation of cyclohexene. The t-butyl hydrogen peroxide (TBHP) was used as oxidant. High cyclohexene conversion (93%) with high 1,2-cyclohexanediol selectivity (98.2%) was obtained over MoO3. Among the tested metal oxide catalysts MoO3, VO5, Nb2O5, Cr2O3, and WO3, MoO3 was found to be the most active catalyst for the oxidation of cyclo-olefins to prepare 1,2-diols. Except cyclohexene oxidation, MoO3 was also found to be active for the oxidation of other cyclo-olefins.

Methyl bromide was synthesized by reacting methane with oxygen and hydrogen bromide over Rh/SiO2 catalyst. The reaction started from the oxidation of HBr to form active bromine species (Br• radicals and Br* surface species), which in turn reacted with CH4 to form CH 3 • radicals and $$\hbox{CH}_{3}^{\ast}$$ surface species. These CH 3 • and $$\hbox{CH}_{3}^{\ast}$$ species reacted with the active bromine species to form CH3Br and CH2Br2. The presence of HBr inhibited the deep oxidation and the steam reformation of CH4 and therefore, guaranteed the high selectivity of CH3Br. In the presence of HBr, CO was formed from the oxidation and steam reformation of CH3Br, while CO2 was formed from the oxidation and steam reformation of CO over Rh/SiO2 at reaction temperature higher than 560 °C.

The metal oxide V 2 O 5 (band gap 2.0 eV) is potentially active in solar light for photocatalysis reactions. However, the rapid electron–hole pair recombination makes it inactive. The doping of V 2 O 5 into MgF 2 (band gap 6.2 eV) matrix reduces the recombination rate of electron–hole pairs and makes VO x /MgF 2 have high photon quantum efficiency (3.2% at 578 nm over 9.1%VO x /MgF 2 for acetone oxidation). The Pt doped 9.1%VO x /MgF 2 catalysts had even higher photon quantum efficiency (34.6% at 578 nm) for acetone oxidation. The VO x /MgF 2 and Pt doped VO x /MgF 2 catalysts were also proved to be active for methanol, ethanol, and benzene photodegradation.

Quaternary ammonium salts were synthesized from ammonium salts and dialkyl carbonates over imidazolium ionic liquid catalysts. The reaction gave almost stoichiometric amounts of the quaternary ammonium salts for halides and nitrates. It was found that the electron-donating property of the alkyl moieties of ammonium cations, the electrophilic nature of the alkyl group of the carbonate, the acidity of the acid that the anion of the ammonium salt corresponds to, and the steric hindrance of the ammonium salts and the dialkyl carbonates are the key factors that influence the yields of quaternary ammonium salts. Strong electron-donating alkyl groups on the nitrogen atom of the ammonium salt, electron-withdrawing groups on the methylene carbon of dialkyl carbonate, and weaker steric hindrance of the starting ammonium salts and dialkyl carbonates favor the alkylation reaction of ammonium salts.

Styrene was oxidized by molecular oxygen over TiO 2 and TiO 2 /SiO 2 for the formation of benzaldehyde. In the absence of catalyst at 100 °C and 10 atm O 2 , polystyrene is the major product. Over the catalysts, the oxidation of styrene is enhanced with benzaldehyde and formaldehyde being the major whereas phenylacetaldehyde, acetophenone, styrene oxide, benzoic acid, and polymer being the minor products. The polymerization of styrene was initiated by the radicals formed in the oxidation reaction. The addition of radical inhibitor nitrobenzene and/or the employment of a catalyst of high specific surface area can promote the termination of the radicals, and hence improve the selectivity of benzaldehyde.

Biological function arises by the assembly of individual biomolecular modules into large aggregations or highly complex architectures. A similar strategy is adopted in supramolecular chemistry to assemble complex and highly ordered structures with advanced functions from simple components. Here we report a series of diamond-like supramolecular frameworks featuring mesoporous cavities, which are assembled from metal-imidazolate coordination cages and various anions. Small components (metal ions, amines, aldehydes, and anions) are assembled into the hierarchical complex structures through multiple interactions including covalent bonds, dative bonds, and weak C-H⋅⋅⋅X (X=O, F, and π) hydrogen bonds. The mesoporous cavities are large enough to trap organic dye molecules, coordination cages, and vitamin B12. The study is expected to inspire new types of crystalline supramolecular framework materials based on coordination motifs and inorganic ions.

Alkanes such as iso-butane, n-pentane, and cyclohexane have been converted effectively to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts below 330 °C. In order to explore the possible reaction pathways, the oxidation of iso-butene, cyclohexene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid were examined over the catalysts. In iso-butene oxidation, acetic acid and 2-methyl maleic anhydride were detected but not maleic anhydride. In cyclohexene oxidation, benzene and phenol were detected as major products but it was not the case in cyclohexane oxidation. The results of our investigation indicate that the oxidation pathway of iso-butane is different from that of iso-butene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid, whereas the oxidation pathway of cyclohexane is different from that of cyclohexene.

A high throughput fluorescence photo-imaging method has been developed for the screening of photo-degradation catalysts. When employed to analyze the photo-degradation of 1,6-hexamethylenediamine (the probe molecule), the method produced results that are comparable to that when methyl orange was employed as a probe molecule and UV spectrometry as an analysis device. We found that the variation trends in catalytic activity over the same group of catalysts are the same in both cases. The results indicate that the fluorescence photo-imaging method is applicable to the screening of photo-degradation catalysts. For comparison, mesoporous catalysts of high specific surface area prepared by using P123 (HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 2 O) 20 H) as a template and “regular” catalysts (those prepared without P123) were tested. The results showed that most of the former catalysts are superior to the latter counterparts. Our study also revealed that the addition of ZrO 2 to TiO 2 did not result in significant improvement in catalytic activities, whereas marked improvement was observed when Nb 2 O 5 or WO 3 was added to TiO 2 . When Nb 2 O 5 and WO 3 were co-doped to TiO 2 , the tertiary catalysts exhibited higher catalytic activities. The catalysts containing 20–30% of Nb 2 O 5 and 10–20% of WO 3 (balanced with TiO 2 ) are superior to any of pure TiO 2 , Nb 2 O 5 , WO 3 , and the binary catalysts composed of any two of TiO 2 , Nb 2 O 5 , and WO 3 . Our study has demonstrated that besides the traditional TiO 2 -domain catalysts, active photo-degradation catalysts can be prepared by combination of Nb 2 O 5 , WO 3 , and ZrO 2 .

Methyl 3,3-dimethoxypropionate was prepared via the oxidation of acrylic acid by oxygen in methanol over PdCl2/CuCl2 catalyst. An acrylic acid conversion of 95.2% with a methyl 3,3-dimethoxypropionate selectivity of 90.6% was obtained at 35 °C and 5 atm. The reaction pathway might be that the esterification of acrylic acid in methanol was the first step, then methyl acrylate reacted with oxygen to form an intermediate aldehyde, which could react with methanol to form methyl 3,3-dimethoxypropionate.

Dimethyl ether is a potential clean fuel and intermediate for other chemical synthesis, such as gasoline, ethylene, and acetic acid. To synthesize dimethyl ether from the traditional syngas process is an energy consuming process. More than one fourth of natural gas must be burned to generate heat for the steam reformation of natural gas. Here, we show a non-syngas process to synthesize dimethyl ether. This process consists of the conversion of methane to bromomethane by reacting methane with hydrogen bromide and oxygen and the hydrolysis of bromomethane to dimethyl ether. Through this process, methane can be high efficiently converted to dimethyl ether.

Acetic acid was synthesized from methane by non-syngas process. In the process, methane was brominated with hydrogen bromide (40 wt.% HBr/H2O) and oxygen to give CH3Br and CO over a Ru/SiO2 catalyst. The as-generated CO and CH3Br reacted with water under the catalysis of RhCl3 to produce acetic acid, methanol, and methyl acetate. In the first step oxidative bromination reaction, 30.1% of methane single pass conversion with 72.4% of CH3Br selectivity and 25.5% of CO selectivity was attained. In the second step, almost 100% CH3Br conversion was reached.

We describe a novel, integrated multi-step process for the partial oxidation of alkanes to alcohols, ethers or olefins using O2 as oxidant. The sequential transformations are (1) alkane bromination to alkyl bromide(s) and HBr, (2) reaction of this mixture with solid metal oxide (MO) to neutralize the HBr and to generate oxygenated products or olefins plus solid metal bromide, and (3) oxidation of the spent solid with O2 to regenerate the metal oxide and Br2 for reuse.

A copper(i)/copper(ii)–salen coordination polymer prepared by solvothermal reactions shows prominent bimetallic catalytic activities towards three-component Strecker reactions and photodegradation of organic dyes under visible-light illumination.

Three 2D luminescent isomeric porous coordination polymers are synthesized and characterized. Their luminescence properties can be modified by grinding and they can act as mechanochromic materials and their properties are probably related to the weak interactions of cuprophilicity and π-π interactions.

Artificial molecular architecture from a large number of subcomponents (50) via self-assembly remains a formidable challenge for chemists. Reaction of 38 components [14 Ni(2+) and 24 N-methyl-1-(4-imidazolyl)methanimine] under solvothermal conditions reproducibly leads to the formation of a high-symmetry coordination cage. This polyhedral cage can also be obtained in high yield by self-assembly of 62 commercially available subcomponents (24 methylamine, 24 4-formylimidazole, and 14 Ni(2+)) under mild conditions involving synchronized formation of both dynamic covalent bonds and coordination bonds. Guest molecules (e.g., water, methylamine, and methanol) are randomly imprisoned in the cage.

The gyroid is ubiquitous for underlying the construction of natural substance and artificial zeolites, but it has been, surprisingly, overlooked by chemists who work in the field of metal-organic frameworks (MOFs). In this work, a series of gyroidal MOFs with gie topology, constructed from 1,2-bis((5H-imidazol-4-yl)methylene)hydrazine and octahedral metal ions, such as Zn(II), Mn(II), Cu(II), and Ni(II), have been synthesized. The Zn(II) analogue, named as STU-1, shows exceptional thermal and chemical stabilities, and exhibits permanent porosity and CO(2) capture ability.

A supramolecular dual emissive system incorporating two classical copper(I)-cluster-based luminophores, namely, Cu(4)I(4) and Cu(3)Pz(3) (Pz = pyrazolate), is reported. The targeted luminescent coordination polymer exhibits reversible thermochromism spanning from green to orange-red.

Catalyst investigation is a typical "trial and error" process. In order to discover a good catalyst, people usually test a huge number of potential catalyst candidates. High-throughput experimentation (HTE) is an efficient methodology for catalyst discovery and optimization. HTE is capable of synthesizing and testing hundreds of catalysts in a short period of time. And it is now becoming a widely applied tool in catalyst discovery and catalyst composition optimization. The development of high throughput experimentation in catalysis includes three steps, which are 1) design and synthesis of catalyst libraries, 2) design of the reactor system for catalytic reactions, and 3) product analysis and data reduction in a high throughput manner. Hence, in this mini-review, the recent developments of high throughput experimentation and these three steps are discussed. The review is focused on the research progress over the last few years.

Centripetally shaped molecules are crystallized with AgSbF(6) to yield coordination networks featuring novel coordination modes, network connectivity and chiral/helical structures.

The partial oxidation of alkanes via bromination followed by the reaction with solid metal oxide mixtures (MO) is shown to give an array of products that can be tuned by varying the MO and the reaction conditions.

Solvothermal subcomponent self-assembly has been employed as a convenient and advanced route to prepare metal-organic frameworks (MOFs). A new gyroidal MOF with gie topology was successfully synthesized and characterized; gas adsorption properties were also investigated.

The solvothermal in situ double cycloaddition reaction of 2-cyanopyrimidine, Cu(2)O and NaN(3) with aqueous ammonia additive generated a two dimensional copper(I) coordination polymer with 5-pyrimidyl-tetrazolate, 3,5-bispyrimidyl-1,2,4-triazolate and the cyano group as the ligands. This reaction can be tuned to yield two dimensional coordination polymers solely based on tetrazolate or 1,2,4-triazolate ligands.