Inorganic Chemistry Communications (v.79, #C)

Contents List (iii-ix).

Among low-cost and earth-abundant elements, the nickel-based HER catalysts, particularly nickel sulfide, are considered as one of the most promising candidates in this field. In this paper, a kind of spherical nickel sulfide material was obtained using nickel acetate and sulfur powder as precursors by one-pot synthesis. The use of sulfur powder as sulfur source with solution-based method will enable the synthesis of metal sulfides to be more simple and capable of mass production. In addition, the as-synthesized nickel sulfide exhibits an onset overpotential of as low as 25 mV, a Tafel slope of 90 mV dec− 1, and an exchange current density of 0.44 mA cm− 2. Furthermore, this catalyst maintains its catalytic activity for at least 25 h and only requires overpotentials of 42 and 113 mV to attain current densities of 2 and 10 mA cm− 2, respectively. The electrocatalytic performance is promising for applications as non-noble-metal HER catalyst with water splitting for hydrogen production.A new nickel sulfide material was successfully synthesized via solvothermal method and characterized by XRD, XPS, SEM and EDS. After conducting an investigation of HER, the nickel sulfide operated with a high catalytic efficiency.Display Omitted
Keywords: Nickel sulfide; Electrocatalytic; XRD; XPS;

Tuning the valence of 3,3-di(1H-tetrazol-5-yl)pentanedioic acid: Solvothermal synthesis of Eu(III) and bimetallic Eu(III)/Cu(II) compounds by Chun Zhai; Meng Yue Guo; Duo Xu; Zhan Yong Yang; Xiao Qing Gu; Qiao Yun Li; Gao Wen Yang (5-7).
3,3-Di(1H-tetrazol-5-yl)pentanedioic acid (H4dtzpda) with four acidic hydrogen atoms can display different valence when reacted with different metal ions. Solvothermal reactions of H4dtapda with Eu(NO3)3·6H2O or Eu(NO3)3·6H2O/Cu(NO3)2·6H2O afford [Eu(Hdtzpda)(H2O)4]·4H2O (1) and [Eu2Cu(dtzpda)2(H2O)10]·6H2O (2), respectively, where only three acidic hydrogen atoms of H4dtzpda are deprotonated in compound 1 while all the four acidic ones are deprotonated in compound 2. In compound 1, Hdtzpda3 − acts as a pentadentate ligand to bridge Eu(III) centers via the oxygen atoms of the carboxylate group while in compound 2, dtzpda4 − is a hepadentate one via not only the oxygen atoms of the carboxylate group but also the nitrogen atoms of the tetrazole rings. The luminescence properties of the two compounds in the solid state show both intraligand and characteristic peaks of Eu3 + at room temperature.3,3-Di(1H-tetrazol-5-yl)pentanedioic acid (H4dtzpda) show different valence when reacted with Eu3 + or bimetallic Eu3 +/Cu2 +. The two compounds with 1D chain intraligand emission and characteristic peaks of Eu3 +.Display Omitted
Keywords: H4dtzpda; Eu(III)/Cu(II); Tunable valence; Crystal structure; Luminescence;

Two Gd2 compounds constructed by 8-hydroxyquinoline Schiff base ligands: Synthesis, structure, and magnetic refrigeration by Wen-Min Wang; Xiao-Fen Guan; Xiao-Di Liu; Meng Fang; Cai-Feng Zhang; Ming Fang; Zhi-Lei Wu (8-11).
Two new Gd2 compounds having formulae, [Gd2(hfac)4(L1)2] (1) and [Gd2(hfac)4(L2)2] (2) (hfac = hexafluoroacetylacetonate, HL1 = 2-[4-methylaniline-imino]methyl]-8-hydroxyquinoline and HL2 = 2-[(3,4-dimethylaniline)-imino]methyl]-8-hydroxyquinoline), have been successfully synthesized via applying two different 8-hydroxyquinoline Schiff base ligands, and further characterized by crystallography. Structural analysis shows that both of 1 and 2 are phenoxo-O bridged dinuclear complexes. The magnetic study reveal that 1 and 2 display cryogenic magnetic refrigeration properties with maximum − ΔS m  = 17.66 J kg− 1  K− 1 at 2 K and 7 T for 1 and − ΔS m  = 14.81 J kg− 1  K− 1 at 3 K and 7 T for 2.Two Gd2 compounds display different cryogenic magnetic refrigeration properties with maximum − ΔS m  = 17.66 J kg− 1  K− 1 at 2 K and 7 T for 1 and 14.81 J kg− 1  K− 1 at 3 K and 7 T for 2.Display Omitted
Keywords: Gd2 compounds; Structure; Magnetic refrigeration;

Significant centre metallic effects on the sensing properties of two isostructural lanthanide metal-organic frameworks by Min-Le Han; San-Tai Wang; Zhong-Qi Li; Zhe Zhou; Dong-Sheng Li; Lu-Fang Ma; Yao-Yu Wang (12-16).
Two isostructural Ln-MOFs, [H2N(CH3)2][Ln(cppa)2(H2O)2] (Ln = Tb/Eu CTGU-1Tb/-1Eu, H2cppa = 5-(4-carboxyphenyl)picolinic acid), were selected to investigate the effects of the different metal centre on the sensing properties. CTGU-1Eu can detect small organic molecule acetone and nitroaromatic explosives in water, whereas CTGU-1Tb can only detect explosive nitrophenol in water.Two isostructural Ln-MOFs were selected to investigate the effects of the different metal centre on the sensing properties. The results reveal that the sensing properties of Ln-MOFs can be adjusted by the different centre metal.Display Omitted
Keywords: Ln-MOFs; Small organic molecule; Nitroaromatic explosives; Sensing properties;

Construction of a novel Cd(II) coordination polymer based on a flexible tripodal carboxylic acid and bimid coligands by Lian Zhou; Kai Zhao; Hao-Yu Dong; Zi-Jun Gao; Yu-Jia Hu; He-Gen Zheng (17-20).
A new coordination polymer was solvothermally prepared based on a semi-rigid multidentate carboxylic acid ligand and benzimidazole (bimid) ligand (H3L = 4,4′,4″-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid): [Cd2(L) (bimid) (DMF)2]·(DMF)3·(H2O)2 (1). The complex 1 was characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetry measurement, elemental analysis and X-ray powder diffraction. Structure analysis reveals that complex 1 displays a rare doubly-interpenetrating (3, 5)-connected hms network with a point symbol {63}{69.8}. Moreover, the fluorescence and gas adsorption properties of the compound 1 were also explored.A new Cd(II) coordination polymer with a rare doubly-interpenetrating (3,5)-connected hms topology exhibits strong fluorescent emission upon excitation at room temperature. The gas adsorption result indicated that compound 1 is potential material for the storage and separation of CO2 and CH4.Display Omitted
Keywords: Metal-organic framework; Cd(II); Crystal structure; Luminescence;

Two new Zn(II)/Cu(II) coordination polymers, [Zn(OPBT)(GA)] n (1) and {[Cu2TTPA(GA)2]·1.5H2O} n (2), have been successfully synthesized from flexible glutaric acid (H2GA) with different bi- and tritopic 1,2,4-triazole derivatives (OPBT = 1.1′-(oxybis(1,4-phenylene))bis(1H-1,2,4-triazole), TTPA = tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine) and Zn(II)/Cu(II) nitrate salts. Their structures have been characterized by infrared spectra, elemental analyses, single crystal and powder X-ray diffraction analyses and thermogravimetric analyses. Both complexes 1 and 2 feature different 2D layers with sql topologies, which can be further arranged ABAB-type, leading to different 3D supramolecular frameworks by C-H···O hydrogen bonding or O-H···O/N hydrogen bonding/π···π stacking interactions. Moreover, the photoluminescence spectra of complex 1 are examined and variable-temperature magnetic susceptibility measurements of complex 2 reveal antiferromagnetic interactions between binuclear Cu(II) ions of paddle-wheel second building units (SBUs).Two new Zn(II)/Cu(II) complexes based on bi- and tritopic 1,2,4-triazole derivatives feature different 2D layers with sql topologies. Moreover, complex 1 exhibits photoluminescence emission and complex 2 reveals antiferromagnetic interactions between binuclear Cu(II) ions.Display Omitted
Keywords: Coordination polymers; Bi- and tritopic ligands; Crystal structures; Luminescent and magnetic properties;

Three copper(I) cyanide coordination polymers, namely [Cu8(CN)8(btmb)2] n (1), [Cu(CN)(btmb)0.5] n (2) and [Cu2(CN)2(dpa)] n (3) (btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, dpa = di(4-pyridyl)amine), were synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectra, PXRD and thermogravimetric analyses. Single-crystal X-ray diffraction analyses reveal that complex 1 is an interesting 2D double-layered network constructing from eight distinct Cu(I) centers, eight μ2-cyanides and two tetradentate cis-btmb ligands. Complex 2 is a ladder-like coordination polymer assembled by CuCN linear chain and bidentate trans-btmb linker. Complex 3 has a 2D wave-like network constructing from CuCN zigzag chain and V-shape dpa spacer. These coordination polymers are thermally stable up to 270–300 °C. They emit blue luminescence originating from ligand-centered emission.Three copper(I) cyanide coordination polymers were constructed based on two flexible N-heterocyclic ligands. [Cu8(CN)8(btmb)2] n (1) is a 2D double-layered network containing eight distinct Cu(I) centers and eight μ2-cyanides. Complex 2 shows a ladder-like chain structure, while complex 3 exhibits a 2D wave-like network. These Cu(I) complexes are stable up to 270–300 °C and emit blue luminescence.Display Omitted
Keywords: Copper(I) complex; Cyanide; N-heterocycle; Crystal structure; Luminescence;

A new cadmium-organic framework fluorescent sensor for Al3 + and Ca2 + ions in aqueous medium by Wenjie Chen; Yanna Lin; Xiaoping Zhang; Na Xu; Peng Cheng (29-32).
A new metal-organic framework (MOF), [Cd2(bptc)(HCOO)]·NH2(CH3)2·3H2O (1), where H4bptc = 3,3′,5,5′-biphenyltetracarboxylic acid, was obtained by solvothermal reaction. The topology of MOF 1 is a (5,8)-connected net with {416  · 58  · 64}{44  · 56}2 point symbol. MOF 1 shows high stability in aqueous solution. Luminescence study indicates that MOF 1 possesses selective turn-on luminescent sensing functions towards Al3 + and Ca2 + ions in aqueous solutions.A new Cd(II) MOF with 3,3′,5,5′-biphenyltetracarboxylic acid was synthesized by solvothermal reaction, which possesses selective turn-on luminescent sensing function towards Ca2 + and Al3 + ions in aqueous solutions.Display Omitted
Keywords: Cadmium-organic framework; Fluorescent sensor; Al3 + ion; Ca2 + ion;

A practical material based on 2,6-dihydroxybenzoic acid: Facile synthesis, strong fluorescence and high-efficiency antibacterial performance by Hua Xiang; Mu-Xiong Lin; Dan-Feng Jian; Sha-Sha Guo; Yi-Xian Gong; Jun Li; Yu Li (33-36).
A terbium complex [Tb(2,6-dhb)3(H2O)4]·2H2O (1) was directly precipitated when reacting Tb(NO3)3·6H2O with 2,6-dihydroxybenzoic acid (2,6-Hdhb) in the presence of KOH. 1 has been characterized by single-crystal X-ray diffraction, EA, FT-IR, PXRD, TG, SEM, UV–Vis, Fluorescence Microscopy and Photoluminescence spectroscopy. The fluorescence properties indicate that 1 shows typical terbium complex emission both in solid state and in organic solutions, along with a luminescence quantum yield of 26.53% in the solid state, indicative of the presence of a quantitative energy transfer from the ligand to the metal. Furthermore, 1 still emits strong green light even after heating in the oven for half an hour. Biological studies reveal that 87% of Escherichia coli cells and 77% of Staphylococcus aureus cells are killed by the aqueous solution of 1. Taken together, facile synthesis, strong and heat-stable fluorescence and high antibacterial capability make 1 a rather practical bifunctional material, showing promise for anti-counterfeiting and biological applications.A practical material [Tb(2,6-dhb)3(H2O)4]·2H2O (1), prepared by a facile, economical and environment-friendly method, has been characterized by single-crystal X-ray diffraction, EA, FT-IR, PXRD, TG, SEM and UV–Vis. 1 shows strong and heat-stable fluorescence with the luminescence quantum yield of 26.53%. Biological studies reveal that 87% of Escherichia coli cells and 77% of Staphylococcus aureus cells have been killed by the aqueous solution of 1.Display Omitted
Keywords: Terbium(III) complex; 2,6-Dihydroxybenzoic acid; Fluorescence properties; Antibacterial activity; Practical material;

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.Display Omitted
Keywords: Metal-organic frameworks (MOFs); Hydrothermal synthesis; Crystal structure; Proton conductivity;

Mononuclear Dy(III) complex based on bipyridyl-tetrazolate ligand with field-induced single-ion magnet behavior and luminescent properties by He-Rui Wen; Fu-Yong Liang; Zheng-Gang Zou; Sui-Jun Liu; Jin-Sheng Liao; Jing-Lin Chen (41-45).
A new mononuclear Dy(III) complex, namely {[Dy(tbpy)2(NO3)(DMF)]⋅ DMF} (1) (tbpy = 6-(tetrazol-5-yl)-2,2′-bipyridine, DMF =  N,N-dimethylformamide), has been synthesized and characterized. Structural measurements reveal that the Dy(III) ion displays a distorted tricapped trigonal prism with two mono-anionic tridentate chelating ligands, nitrate anion and N,N-dimethylformamide molecule. Magnetic investigation indicates that the title complex 1 exhibits field-induced single-ion magnet behavior. Moreover, the studies on photoluminescence properties show that complex 1 displays relatively strong fluorescent emission, which are typical narrow emission bands of lanthanide ion.A new mononuclear Dy(III) complex based on bipyridyl-tetrazolate ligand has been synthesized and characterized. The title complex displays field-induced single-ion magnet behavior and relatively strong fluorescent emissions.Display Omitted
Keywords: Dy(III) complex; Single-ion magnet; Slow magnetic relaxation; Luminescent properties;

A porous the-type metal-organic framework based on [Mn4Cl]7 + clusters for selective gas sorption by Qing-Hua Meng; Jing-Li Liu; Xu Long; Shuan Zhang; Yan Quan (46-49).
An anionic cage-type metal–organic framework, {(Me2NH2)5[Mn4Cl(BTB)4(H2O)4](DMF)2(EtOH)7}n (1, DMF =  N,N-Dimethylformamide), has been successfully prepared by the reaction of MnCl2 with trigonal planar 4,4′,4″-benzene-1,3,5-triyl-tri-benzoic acid (H3BTB) ligand under solvothermal conditions. Its structure was characterized by single-crystal X-ray diffraction techniques, which reveal that it is constructed by cross-linking BTB3 − ligands with the in situ-generated square-planar [Mn4Cl]7 + secondary building units. The free space of 1 is formed by packing of octahedral and cuboctahedral cages, and the overall framework exhibits a 2-fold interpenetrated the -type topology. N2 adsorption isotherm at 77 K confirmed the permanent porosities of the activated 1 and the variable-temperature adsorption measurements of CO2 and CH4 revealed its high adsorption abilities of CO2 over CH4 at room temperature.An anionic cage-type metal–organic framework was successfully prepared by using the 4,4′,4″-benzene-1,3,5-triyl-tri-benzoic acid (H3BTB) ligand under solvothermal conditions, whose framework is constructed by cross-linking BTB ligands with in situ-generated square-planar [Mn4Cl]7 + secondary building unit. The free space of this MOF is formed by packing of octahedral and cuboctahedral cages, and the overall framework exhibits a 2-fold interpenetrated the -type topology. N2 adsorption isotherms at 77 K confirmed its permanent porosity and variable temperature adsorption measurements of CO2 and CH4 revealed its potential application in the CO2/CH4 separation progress.Display Omitted
Keywords: Cage-based MOF; the-type topology; Square-planar SBU; Selective gas sorption;

A highly selective and sensitive Schiff-base based turn-on optical sensor for Cu2 + in aqueous medium and acetonitrile by Xin Wang; Wei Shi; Lei Feng; Junchi Ma; Yuqin Li; Xiangjuan Kong; Yabin Chen; Yonghai Hui; Zhengfeng Xie (50-54).
A simple “turn-on” fluorescence chemosensor L (E)-2-((4-(diphenylamino)benzylide-ne)amino)phenol has been synthesized, which displays a rapid, highly sensitive and selective detection for Cu2 + ions amongst other metal ions. The association constant for L-Cu2 + complex determine from Benesi–Hildbrand plot was found as 1.96 × 107  M− 1 and 5.43  ×  107  M− 1 with the detection limit of 1.8 × 10− 7  M and 8.5 × 10− 7  M in CH3CN and CH3CN/H2O (v/v = 4/6, pH = 7.4) HEPES buffer, respectively. Potential application of L for Cu2 + detection in real water samples was also investigated.Display Omitted
Keywords: Schiff-base; Cu2 + sensor; Fluorescence enhancement; Blue shift;

A novel adenine-based zinc(II) metal-organic framework featuring the Lewis basic sites for heterogeneous catalysis by Shixing Zhang; Hongming He; Fuxing Sun; Nian Zhao; Jianshi Du; Qinhe Pan; Guangshan Zhu (55-59).
Metal-organic frameworks (MOFs), as a new sort of crystalline materials, have attracted lots of interest in many applications during the past decades. Recently, many efforts have been focused on the development of MOFs as heterogeneous catalysis. In this communication, we selected adenine (ad) and tetracarboxylic acid, namely 5,5′-(1,3,6,8-tetraoxobenzo[Imn] Li et al. (1999), He et al. (2016) phenanthroline-2,7-diyl)bis-1,3-benzenedicarboxylic acid (H4L), as organic linkers to assemble with Zn(II) ions to construct a novel adenine-based porous MOF. There are three different inorganic clusters in the framework, including ZnO2N2, Zn2O2N6, and ZnO5N clusters. Interesting, the resultant porous MOF, namely [H2N(CH3)2]⋅[Zn4(L)1.5(ad)3(H2O)2]⋅ 4DMF, retains free amino groups in the framework, which can be served as Lewis basic sites to catalyse Knoevenagel condensation reaction. The catalytic study exhibits that the as-synthesized MOF with free amino groups can be used as heterogeneous catalysis with remarkable catalytic efforts and good recycle.A novel adenine-based zinc(II) MOF has been formed by mixing ligands, which can be used as base catalyst for the Knoevenagel condensation reaction.Display Omitted
Keywords: Metal-organic framework; Adenine; Amino group; Catalysis; Knoevenagel reaction;

A new “turn-on” fluorescent sensor for highly selective sensing of H2PO4 by Ping-Xiao Liu; He Chen; Ning Xu; Hai-Ning Wang; Xing Meng; Zi-Yan Zhou; Zhong-Min Su (60-64).
H2PO4 plays an indispensable role in chemical, biological and environment aspects. It is essential to detect H2PO4 sensitively. In this article, we designed and synthesized a novel sensor P-Fe based on naphthalimide. Hence, P-Fe can selectively and sensitively detect H2PO4 ion by means of “turn-on” detection. After adding H2PO4 , the P-Fe solution gives a strong bright yellow fluorescence. In addition, the corresponding detection limit of P-Fe to H2PO4 is estimated to be 1.897 × 10− 7  mol/L.We designed and synthesized a novel sensor P-Fe based on Schiff base. The P-Fe solution gives a strong bright yellow fluorescence after adding H2PO4 . Hence, P-Fe can selectively and sensitively sense H2PO4 ion by means of “turn-on” detection. The detection limit of P-Fe to H2PO4 is 1.897 × 10− 7  mol/L.Display Omitted
Keywords: Schiff base; Fluorescence sensor; H2PO4 detection;

The aim of this work was to investigate the structure/property correlation in metal-organic framework thin films, in particular MOF-199, toward the decolorization of harmful organic dye reactive red 198. MOF thin films were fabricated on bare and surface-modified TiO2 substrates using a layer-by-layer deposition technique. Our results indicate that the preferentially-oriented MOF grown on DHBA-functionalized titania sublayer exhibits better photocatalytic activity due to its capability of absorbing a broader range of light. These films also exhibit an orientation-dependent adsorption behavior. While the MOF with oriented crystallites shows bigger adsorption capacity, its initial (kinetic) adsorption was lower when compared to the film grown on bare substrate.Display Omitted
Keywords: Metal-organic frameworks; Thin films; Crystal structure; Adsorption; Photocatalysis; Reactive red 198;

Metal-organic fameworks based on multi-carboxylate ligands with threefold symmetries and luminescence properties by Man Zhu; Meng-Ting Li; Liang Zhao; Kui-Zhan Shao; Zhong-Min Su (69-73).
Three new metal–organic frameworks, namely, [Cd1.5(tcpb)(DMF)(H2O)] (1), [Co1.5(tcpb)(DMF)2]·3DMF (2) and [Zn(Htcpb)(4,4′-bpy)0.5]·1.5H2O (3) (tcpb = 1.3,5-tris(4-carbonylphenyloxy)benzene) have been synthesized by solvent-thermal method. The single-crystal X-ray diffraction analysis shows that compound 1 is 2D grid layers, with the trinuclear cadmium clusters acting as secondary building units (SBUs), and the tcpb ligand serveing as organic linkers. Compound 1 and Compound 2 are isomorphic structures containning similar connection modes of tcpb ligands with trinuclear metal clusters. Compound 3 is a 3D interpenetrated framework based on dinuclear Zn cluster with dia topology. The fluorescence properties for solid state compound 1 and 3 were examined at room temperature. Compared with free tcpb ligands, both of them display remarkable red-shift.Three new metal-organic frameworks constructed from d10 metal and 1,3,5-tris(4-carbonylphenyloxy)benzene (tcpb) were synthesis under solvothermal condition. Compound 1 and 2 are 2D grid layers, in which the trinuclear metal clusters act as secondary building units (SBUs), and the tcpb ligand serves as organic linkers. Compound 3 is a 3D interpenetated structure with dia topology based on dinuclear Zn cluster as SBUs. All these frameworks had good stability in the air and Compound 1 and 3 exhibited strong photoluminescence at room temperature.Display Omitted
Keywords: Metal–organic frameworks; supramolecular polymers; interpenetrated network; Luminescence;

Metal organic framework Cu/MIL-53(Ce)-mediated synthesis of highly active and stable CO oxidation catalysts by Hai-Yan Tan; Yin Zhou; Yun-Fan Yan; De-Yong Wu; Wei-Bing Hu; Xin-Yu Shi (74-77).
The highly dispersed CuO@CeO2 catalysts were produced from Cu/MIL-53(Ce) through encapsulated copper in a matrix of metal organic framework MIL-53(Ce), serving as a catalyst for CO oxidation. Comparison on the catalytic performance between the CuO@CeO2 and the (CuO or MIL-53(Ce)) catalytic material has been conducted to understand the catalytic behavior of the catalysts. The CuO@CeO2 catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), N2 adsorption-desorption, and the hydrogen temperature-programmed reduction (H2-TPR). The analyses indicated that the unique CuO@CeO2 spatial confinement in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation. Indeed, the heterogeneous catalytic composite materials CuO@CeO2 catalyst exhibited excellent activity in CO oxidation test, with 100% conversion at 79–95 °C and the catalytic activity were stable after reaction 300 h.The highly dispersed CuO@CeO2 nanoparticles, which resulted from the CuO uniformly supported on the three dimension porous structure of MIL-53(Ce), give rise to a superior catalytic activity and stability for CO oxidation.Display Omitted
Keywords: Metal-organic framework; Cu/MIL-53(Ce); Calcination; CuO@CeO2 catalyst; CO catalytic oxidation;

Controlled release of drug molecules in metal–organic framework material HKUST-1 by Qing Chen; Qi-Wei Chen; Chong Zhuang; Piao-Ping Tang; Ning Lin; Lian-Qiang Wei (78-81).
The Cu3(BTC)2 metal–organic framework (MOF) (BTC = 1,3,5-benzenetricarboxylate), also known as HKUST-1, is one of the earliest reported stable MOFs with a very high surface area. In this study, HKUST-1 was used for the first time to absorb the pharmaceutical products of ibuprofen, anethole and guaiacol with loading amount of 0.34 g·g− 1, 0.38 g·g− 1 and 0.40 g·g− 1, respectively, which also showing good controlled drug release property. The result from this work provides a new attempt for HKUST-1 to be used as potential platform for drug delivery and release.In this study, HKUST-1 was used for the first time to absorb the pharmaceutical products of ibuprofen, anethole and guaiacol, the drug loading amount were 0.34 g·g− 1, 0.38 g·g− 1 and 0.40 g·g− 1, respectively, which also showing good controlled drug release property.Display Omitted
Keywords: Metal organic frameworks; HKUST-1; Drug delivery; Controlled release;

Open-chain hemiketal is stabilized by coordination to a copper (II) by Anna A. Melekhova; Alexander S. Novikov; Nikolai V. Rostovskii; Pavel A. Sakharov; Taras L. Panikorovskii; Nadezhda A. Bokach (82-85).
The hemiketal complex [Cu{NH2C(Me)2C(Ph)(OMe)O}2] (1) was generated by the reaction of [Cu(NCMe)4](BF4) and 4 equivs of 2,2-dimethyl-3-phenyl-2H-azirine in the presence of NCNMe2 in wet MeOH and isolated in 92% yield. In 1, the in situ formed hemiketal NH2C(Me)2C(Ph)(OMe)OH in its deprotonated form is stabilized due to chelation to copper(II). In the X-ray structure of 1 •4MeOH, the intermolecular hydrogen bonding was detected between O and N atoms of the organic ligand and the H―O group of solvated MeOH as well as between two molecules of the solvated MeOH. Three types of hydrogen bonds in the obtained structure were studied by the DFT calculations (M06/6-31 ++G** level of theory, MDF10 pseudopotentials on the Cu atoms) and topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method). Estimated strength of these non-covalent interactions is 3–9 kcal/mol.The in situ formed hemiketal NH2C(Me)2C(Ph)(OMe)OH in its deprotonated form is stabilized due to chelation to copper(II).Display Omitted
Keywords: Copper complexes; 2H-Azirines; Ligand reactivity; Hemiketals; Hydrogen bonding;

Using an asymmetrical Cr(III)-bis-Schiff-base complex [Cr(L)Cl] (1; H2L obtained from condensation of 5-bromo-salicylaldehyde and HL0 ((Z)-4-((2-aminophenylimino)(phenyl)methyl)-3-methyl-1H-pyrazol-5(4H)-one) as the catalyst, bulk solvent-free ring-opening copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride) in the presence of cocatalyst DMAP (4-(dimethylamino)-pyridine) was effectively realized, in which, on the condition of low 1/DMAP concentration for a controllable polymerization, perfectly alternating polyester while not poly(ester-co-ether) could be obtained.An asymmetrical Cr(III)-bis-Schiff-base complex [Cr(L)Cl] (1) in combination with DMAP is found to effectively catalyze bulk solvent-free copolymerization of CHO and MA, and their low concentrations can produce the perfectly alternating polyester in a controllable mode.Display Omitted
Keywords: Cr(III) asymmetrical bis-Schiff-base complex; Polyester; Poly(ester-co-ether); CHO and MA; Bulk solvent-free copolymerization;

New cyclometalated ruthenium(II) complexes of the type [Ru(L)(CO)(EPh3)2] (L = di-anionic CNO- donor of 1-(biphenylazo)naphthol; E = P, As) have been synthesized by the reaction using [RuHCl(CO)(EPh3)3] (E = P, As) with 1-(biphenylazo)naphthol ligand (H2L). The 1-(biphenylazo)naphthol ligand and ruthenium complexes are characterized by analytical, spectral (FT–IR, UV–Vis, 1H NMR and 31P NMR) methods. The molecular structure of ruthenium complex 1 was further confirmed by single crystal X-ray diffraction method. The catalytic efficiency of ruthenium complex 1 was evaluated for the transfer hydrogenation of various ketones to alcohols with excellent conversion up to 99% in the presence of i-PrOH/KOH at 82 °C.Display Omitted
Keywords: C − H activation; Ruthenium(II) complexes; Crystal structure; Transfer hydrogenation;

A new inorganic-organic open framework based on Wells-Dawson arsenomolybdate, {Ag(diz)2}3[{Ag(diz)2}3(As2Mo18O62)]∙H2O (1) (diz = 1,2-diazole) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, UV, XRD, and single-crystal X-ray diffraction. In compound 1, each {As2Mo18} cluster uses six terminal oxygen atoms on 'equator' position to attract peripheral six {Ag(diz)2} linkers, which are further connected by six Dawson clusters located on two different planes via unique equator-to-equator interlaced ways to form a unprecedented 3D network with {812  ∙ 123}{8}3 topology. Compound 1 represents the highest covalent connectivity of 3-D Dawson arsenomolybdate, which exhibits merit photocatalytic properties for degradation of refractory dyes Azon Phloxine (AP) under UV light. In addition, compound 1 has a potent inhibition effect on proliferation of Human gastric adenocarcinoma cells (SGC-7901).The silver organic complex linkers {Ag(diz)2} are introduced into {As2Mo18} systems, leading to unprecedented 3-D network with {812  ∙ 123}{8}3 topology, which represents the highest covalent connectivity of 3-D Dawson arsenomolybdate. The compound exhibits high-efficient degradation ability for refractory dyes AP and potent inhibition effect on proliferation of SGC-7901 cells.Display Omitted
Keywords: Hydrothermal synthesis; Arsenomolybdate; Photocatalytic properties; Anticancer activity;

Solar-light driven photocatalytic conversion of p-nitrophenol to p-aminophenol on CdS nanosheets and nanorods by Azam Khan; Zia-ur- Rehman; Abdullah Khan; Hina Ambareen; Haseeb Ullah; Syed Mustansar Abbas; Yaqoob Khan; Rajwali Khan (99-103).
A simple synthetic protocol devoid of toxic surfactants was applied for the synthesis of CdS nanosheets and nanorods by thermolyzing bis(4-benzylpiperadine-1-carbodithioate-κ2 S, S′) cadmium(II) (1) and propane-1,3-diyl bis (piperidincarbamodithioate)cadmium(II) (2) using ethylenediamine (en) as a solvent. The as obtained products were characterized by TEM, PXRD, and UV–Visible spectroscopy. The nanosheets (1) and nanorods (2) were confirmed by HR-TEM with a lattice spacing of 0.33 nm which corresponds to the 002 plane of hexagonal CdS, observations in consonance with XRD. Based upon the band gap obtained from UV–Vis, 2.91 eV (nanosheets) and 2.65 eV (nanorods), these nanoparticles (NPs) were used as solar light driven photocatalyst for the conversion of p-nitrophenol to p-aminophenol. The nanorods (8 min) were found slightly more efficient than nanosheets (10 min), and the conversion efficiency of both remained above 92% even after 3rd cycle without any structural damage as revealed by the afterward PXRD. The better catalytic activity of both morphologies can be attributed to quantum size effect and good optical absorbance.Display Omitted
Keywords: CdS; Nanosheets; Nanorods; Mechanism of NPs formation; Photocatalysis; p-Nitrophenol;

Synthesis, structure and electronic calculation of alkali metals borate Li2Na[B5O8(OH)2] by Qian Wang; Li Wang; Dan-Dan Zheng; Bing-Bing Zhang; Zulipiya Abulizi; Shi-Lie Pan; Tao Yang (104-108).
A new alkali metals borate complex, Li2Na[B5O8(OH)2], has been successfully synthesized by a facile hydrothermal method. Single-crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic space group Pbcn with a  = 8.919(3) Å, b  = 9.181(3) Å, c  = 8.416(2) Å, Z = 4. The crystal structure is constructed of two dimensional (2D) [(B5O8)(OH)2] layers, while stacking along b axis and then connected by Li+ and Na+ cations to extend to 3D framework Li2Na[B5O8(OH)2]. UV-vis-NIR spectrum shows that Li2Na[B5O8(OH)2] possesses a wide range of transparency and a UV cut-off edge below 190 nm which indicates that it may be applied in the deep ultraviolet region. The calculated band structures and the density of states indicate that Li2Na[B5O8(OH)2] is a direct band gap compound with a band gap of 5.68 eV. In addition, IR spectroscopy, thermal stability and theoretical calculations of Li2Na[B5O8(OH)2] are also reported in this work.A new alkali metals borate complex, Li2Na[B5O8(OH)2] has been successfully synthesized. It a direct band gap compound with a band gap of 5.68 eV and possesses a UV cut-off edge below 190 nm.Display Omitted
Keywords: Borate; Deep ultraviolet; Hydrothermal reaction;