Inorganic Chemistry Communications (v.56, #C)

Contents List (iii-xi).

Two new coordination polymers, [Zn2(cptpy)2Cl2]n·0.5nH2O (1) and [Cd2(cptpy)4]n·3.5nH2O (2) (Hcptpy = 4′-(4-carboxyphenyl)-4,2′:6′,4″-terpyridine), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 shows a new two-fold interpenetrating 3-connected 2D framework with the hcb topological net and the Schläfli symbol of 63. Compound 2 displays a two-fold interpenetrating (4,4)-connected 2D framework with the sql topological net and the Schläfli symbol of {44  · 62}. Interestingly, compounds 1 and 2 were obtained in the similar reaction conditions. The structural diversity of compounds 1 and 2 may illustrate the marked effect of the metal ion of the reaction solution. Additionally, photoluminescence properties of compounds 12 have been investigated.Two new 2-fold interpenetrating Zn/Cd coordination polymers based on a bis-functioned trigonal ligand have been synthesized by changing metal ion under hydrothermal reactions, giving topological networks those of 2D structures. The thermal stability and luminescent property have been investigated.Display Omitted
Keywords: MOFs; d10 metal; Terpyridine derivative; Crystal structure; Luminescent property;

Two new Gd(III) complexes 1 and 2 of the type [Gd(L)H2O]·nH2O were synthesized from DTPA-bis(amide) conjugates of arylpiperazinyl amines. The relaxivity (R 1) of these complexes was measured in deionized water, which revealed that complex 2 had a higher relaxivity than 1 and Omniscan®, a commercially available MRI contrast agent. The cytotoxicity studies of 1 and 2 indicated that they are non-toxic which warrant their physiological suitability as potential contrast agents for MRI. All the synthesized ligands and complexes were characterized with the aid of analytical and spectroscopic methods including elemental analysis, 1H NMR, FT-IR, XPS and fast atom bombardment (FAB) mass spectrometry.Two new Gd(III) complexes 1 and 2 of the type [Gd(L)H2O]·nH2O were synthesized. The relaxivity (R 1) of these complexes revealed that 2 had a higher relaxivity than 1 and Omniscan®. The cytotoxicity studies of 1 and 2 indicated that they are non-toxic which warrant their suitability as potential contrast agents for MRI. All the synthesized ligands and complexes were characterized by elemental analysis, 1H NMR, FT-IR, XPS and FAB mass spectrometry.Display Omitted
Keywords: DTPA-bis(amide); Arylpiperizine; Gd(III)-complexes; Relaxivity; MRI contrast agents;

Two new pH-controlled coordination polymers constructed from an asymmetrical tricarboxylate ligand and Zn-based rod-shaped SBUs by Wei-Ping Wu; Bo Liu; Guo-Ping Yang; Hui-Hui Miao; Zheng-Ping Xi; Yao-Yu Wang (8-12).
Two new 3D coordination polymers, [Zn3(L)2(H2O)4]·H2O (1) and [Zn5(μ 3-OH)4(L)2(H2O)2] (2) (H3L = 3-(2′,5′-dicarboxylphenyl)benzoic acid), have been synthesized under hydrothermal conditions by adding different amounts of NaOH. Structural analyses show that both of them contain 1D inorganic Zn(II)-chains as rod-shaped secondary building units (SBUs) but they are in different forms. The rod-shaped Zn(II)-chain of 1 is only Zn-carboxylate chain, while the one in 2 is formed by the independent Zn5(COO)6 clusters connected by hydroxyl oxygen. Furthermore, the thermal and luminescent properties of both compounds have been studied.Two new coordination polymers based on two different rod-shaped SBUs have been synthesized by controlling the amount of NaOH added. Particularly, an unusual rod-shaped Zn-chain is formed by the independent Zn5(COO)6 clusters connected by OH groups. This work presents that NaOH not only regulates the pH but also can participate in coordination.Display Omitted
Keywords: Coordination polymers; pH-controlled; Rod-shaped SBUs; Luminescence;

A sandwich-type tungstoantimonate containing trinuclear nickel ions modified with aminopyrazine ligand by Lizhou Wu; Bin Liu; Xinbo Dong; Chengxing Yu; Yonghong Yan; Huaiming Hu; Ganglin Xue (13-16).
A new organic–inorganic hybrid tungstoantimonate, Na4[Ni2(apy)(H2O)10]1/2[(Ni(Hapy))3(Na(H2O)2)3(SbW9O33)2]·23H2O (1) (apy = aminopyrazine), has been synthesized and fully characterized. Single crystal X-ray diffraction analysis indicates that the polyanion [(Ni(Hapy))3(Na(H2O)2)3(SbW9O33)2]6 − displays a sandwich-type dimeric structure in which the Ni2 + ions in the central belt are modified by aminopyrazine ligands. The contrast experiment analyses show that the existence of organic amine ligand is a key role to the formation of the stable Hervé-type tungstoantimonate containing trinuclear nickel(II) ions, which crystallized with dinuclear nickel complex constructed from an aminopyrazine bridging two [Ni(H2O)5]2 + ions as part of counterions. The variable-temperature magnetic measurements of 1 exhibit the weak antiferromagnetic exchange interactions among Ni(II) clusters in 1.A new Hervé-type tungstoantimonate containing trinuclear nickel ions modified with aminopyrazine ligand to substitute coordinated water molecules attached to nickel ions has been synthesized and fully characterized.Display Omitted
Keywords: Polyoxometalate; Tungstoantimonate; Nickel; Aminopyrazine; Magnetism;

Investigation of antibacterial activity and related mechanism of a ruthenium(II) polypyridyl complex by Dongdong Sun; Weiwei Zhang; Endong Yang; Nuan Li; Haiping Liu; Weiyun Wang (17-21).
Metal based drug represents a novel group of antimicrobial agents with potential application for the control of bacterial and fungal infections. In this study, we fabricate ruthenium(II) complex containing the polypyridyl ligands, namely [Ru(phen)2(tip)] (ClO4)2 (RuTh) and carefully investigate its antibacterial activities against both the Gram-negative (G −) bacteria Escherichia coli (E. coli) and the Gram-positive (G +) bacteria Staphylococcus aureus (S. aureus). The RuTh is more toxic to S. aureus than that to E. coli. The antibacterial effects of RuTh are further investigated, revealing specific mechanisms. The results demonstrate that RuTh functions as a bactericide against the E. coli and S. aureus through disrupting bacterial cell wall integrity and its cellular components.We fabricate ruthenium(II) complex containing the polypyridyl ligands, namely [Ru(phen)2(tip)] (ClO4)2 and carefully investigate its antibacterial activities against both the Gram-negative bacteria E. coli and the Gram-positive bacteria S. aureus.Display Omitted
Keywords: Ruthenium(II) complexes; Antibacterial activity; Cellular uptake; Cell morphology;

Synthetic methods, structural features, and exciting properties of some novel mono-, di- and polynuclear compounds with benzidine as ligands are described in this short review.Syntheses, structural diversity and exciting properties of a set of mono-, di- and polynuclear coordination compounds of benzidine binding towards different transition and nontransition metal ions have been delineated in this review. The long-range structures in terms of different weak non-covalent forces in the crystalline states are also highlighted.Display Omitted
Keywords: Metal-ions; Benzidine; Syntheses; Structures; Properties;

A novel Dawson-like cerium(IV)-hybridizing selenotungstate Na13H7[Ce(SeW17O59)2]·31H2O by Hailou Li; Wen Yang; Yun Chai; Lijuan Chen; Junwei Zhao (35-40).
A novel cerium(IV)-hybridizing selenotungstate with Dawson-like structure Na13H7[Ce(SeW17O59)2]·31H2O (1) has been synthesized by reaction of Na2WO4·2H2O, Na2SeO3 and (NH4)2Ce(NO3)6 in the aqueous solution and characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. To the best of our knowledge, 1 stands for 1:2-type Dawson-like selenotungstate constructed from two identical [SeW17O59]12 − moieties combined via one Ce4 + ion. The Ce4 + cation displays a distorted square prismatic geometry defined by eight oxygen atoms from two [SeW17O59]12 − moieties. In the [Ce(SeW17O59)2]20 − polyoxoanion, the {SeO3} trigonal pyramid encapsulated into the [SeW17O59]12 − fragment is situated on the side close to the Ce4 + ion. The TGA curve of 1 reveals two steps of weight loss between 25 °C and 700 °C. Furthermore, the electrochemical and the electrocatalytic properties of 1 have been measured by cyclic voltammetry (CV) in 0.5 M Na2SO4  + H2SO4 aqueous solution.A novel Dawson-like cerium(IV)-hybridizing selenotungstate Na13H7[Ce(SeW17O59)2]·31H2O (1) has been synthesized and characterized.Display Omitted
Keywords: Polyoxometalate; Selenotungstate; Dawson-like polyoxoanion; Electrochemistry;

Herein we report the first charge-transfer metal–organic framework with open Cu(I)-sites, which exhibits intriguing solvent-dependent luminescence behaviors. An extended analysis of experimental and computational result indicates that strong metal–solvent bonding interaction plays a dominant role in the sensing of various solvents.A new charge-transfer metal–organic framework with open Cu(I)-sites has been obtained, which exhibits intriguing solvent-dependent luminescence behaviors. An extended analysis of experimental and computational result indicates that strong metal–solvent bonding interaction plays a dominant role in the sensing of various solvents.Display Omitted
Keywords: Copper(I) cyanide; Crystal structure; Luminescence; Quantum chemical calculation;

Synthesis, crystal structure and characterization of trivacant-Keggin-polyoxometalate-based carbonyl manganese derivative by Yinbao Liu; Yanhui Zhang; Pengtao Ma; Yongkang Dong; Jingyang Niu; Jingping Wang (45-47).
A novel trivacant polyoxometalate-based carbonyl manganese derivative, (NH4)3H3[{Mn(CO)3}(Mn(H2O)2)(Mn(H2O)3)(TeW9O33)]2·31H2O (1), was successfully isolated in the mixed solvent of acetonitrile and water at room temperature. The composition and structure of the product were characterized by elemental analysis, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), IR, UV–vis, CV and single crystal X-ray diffraction.A novel polyoxometalate-based carbonyl manganese derivative, (NH4)3H3[{Mn(CO)3} (Mn(H2O)2) (Mn(H2O)3)(TeW9O33)]2·31H2O (1), was successfully isolated and further characterized by elemental analysis, X-ray powder diffraction (XRPD), thermogravimetric analyses (TG), IR, UV–vis, CV and single crystal X-ray diffraction.Display Omitted
Keywords: Polyoxometalate; Carbonyl manganese;

Assembly of a semi-rigid tripodal ligand, 3,5-bis(4-carboxyphenoxy)benzoic acid (H3bpa), with Ln2O3 (Ln = Dy for 1 and Er for 2) under hydrothermal condition produces two three-dimensional (3-D) lanthanide–organic frameworks (LnOFs), [Dy2(bpa)2(H2O)3] (1) and [Er4(bpa)4(H2O)6](H2O) (2). Single crystal X-ray diffraction indicates that LnOFs 1 and 2 involve different one-dimensional (1-D) rod-shaped metal-carboxylate secondary building units (SBUs), which are further extended to afford two different 3-D frameworks via the linkage of bpa3 − ligands. The results demonstrate that the diverse conformations and coordination modes of bpa3 − ligands play a key role on the formation of the final framework structures. Temperature-dependent magnetic susceptibility measurements reveal the presence of LnIII⋯LnIII ferromagnetic interactions in both LnOFs.The construction of two magnetic 3-D DyIII and ErIII lanthanide–organic frameworks has been successfully achieved based on 3,5-bis(4-carboxyphenoxy)benzoate, and their diverse framework structures can be well regulated by different infinite 1-D rod-shaped inorganic [Ln x (COO) y (H2O) z ] SBUs.Display Omitted
Keywords: LnOFs; Tripodal multicarboxylate ligand; Rod-shaped SBUs; Magnetic properties;

Mono- and heterometallic europium (III) and terbium (III) complexes: Synthesis, crystal structures and luminescent properties by Yan-Ju Xiong; Pei-Ling Huang; Xiao-Wei Zhang; Wei-Yan Huang; Qiu-Hong Huang; Qian Cheng; Jie-Fang Fang; Yun Li; Fei-Fei Zhu; Shan-Tang Yue (53-57).
Four new rare earth organometallic coordination polymers [EuIII(Hbidc)(pdc)·2(H2O)]2·4H2O (1), [TbIII(Hbidc)(pdc)·2(H2O)]2 (2), and {[LnIIIAgI(bidc)(pdc)·2(H2O)]}n·H2O (Ln = Eu (3), Tb (4)) (H2bidc = 1H-benzimidazole-5,6-dicarboxylic acid, H2pdc = 2,6-pyridine dicarboxylic acid) have been synthesized through self-assembly reactions. The X-ray single crystal diffraction indicates that these complexes are isomorphous, namely triclinic P − 1. Interlayer O–H⋯O and C–H⋯O hydrogen bonding has been observed in the structure of four complexes, generating 1D zigzag infinite chain, 2D plane layer, and even 3D ladder-like supramolecular framework. Addition of silver nitrate to chemicals leads to massive restructuring and emission intensity enhancement of complexes 3 and 4. Furthermore, thermal stabilities and luminescent of 14 have also been discussed in detail.Addition of silver nitrate to chemicals in 1 and 2 leads to massive restructuring and emission intensity enhancement of complexes 3 and 4.Display Omitted
Keywords: Eu(III); Tb(III); Crystal structures; Luminescent properties; Hydrogen bonding;

The syntheses, characterizations and properties of two coordination complexes, [Cr3(L)3Cl6] (1) and [Cu4(L)2Br2]n (2) (HL = 2,2′,2″-(1H-imidazole-2,4,5-triyl)tripyridine) were reported. The HL ligand was unprecedentedly afforded by metal-mediated solverthermal in situ metal–ligand reaction among picolinaldehyde, ammonium acetate and metal ions. Compound 1 can be described as a bottom-opened vase-like complex with the three CrIII ions showing a triangle conformation. For complex 2, the sandwich-like [Cu4(L)2]2 + moieties are linked by bromide ions to generate a 1D chain framework. Variable-temperature magnetic studies in the temperature range of 2.0–300 K for 1 reveal antiferromagnetic CrIII⋯CrIII interactions. The catalytic activity of 2 towards the reaction of 2-butanone and ethylene glycol was also investigated; it showed a very good catalytic property allowing for the easy and high yielding preparation of 2-ethyl-2-methyl-1,3-dioxolane under mild conditions.Solvothermal in situ metal ligand reaction of picolinaldehyde, ammonium acetate and metal ions leads to generation of two structurally interesting coordination complexes supported by 2,2′,2″-(1H-imidazole-2,4,5-triyl)-tripyridine.Display Omitted
Keywords: In situ metal–ligand reaction; 2,2′,2″-(1H-imidazole-2,4,5-triyl)tripyridine; Magnetic properties; Catalytic activity;

Structure and magnetism of novel dinuclear cobalt(II) complexes by Jakub Mihalčiak; Petra Bertová; Zdeňka Růžičková; Ján Moncol; Peter Segľa; Roman Boča (62-64).
Two dinuclear cobalt(II) complexes of the formula [Co2X4(isonia)4] have been synthesized and structurally characterized; isonia is unidentate neutral iso-nicotinamide and X are furan-3- or furan-2-carboxylate ligands. The chromophore {CoO4N2} is formed of two iso-nicotinamide ligands and three furancarboxylate ligands where two of them bear a bridging function and one is a terminal-bidentate ligand. The magnetic data confirm a weak exchange interaction (J  /  hc  = − 2 cm− 1) and a high single-ion zero-field splitting (D  /  hc  = 63 and 33 cm− 1, respectively).[Co2(3-furancarboxylate)4(iso-nicotinamide)4]–hydrogen bonding network in a structure of 1D supramolecular chain created by a new binuclear complex.Display Omitted
Keywords: Cobalt(II) complex; Crystal structure; Exchange coupling; Zero-field splitting;

[P2V3W15O62]9 − cluster based covalent polyoxometalate-organic hybrid: Synthesis, structure, self-assembly and in vitro antioxidant activities by Pulikanti Guruprasad Reddy; V.S.V. Satyanarayana; Vinay Dubey; Asit Ranjan Ghosh; Chullikkattil P. Pradeep (65-68).
A new [P2V3W15O62]9 − cluster based covalent polyoxometalate-organic hybrid (P1) containing a naphthol-amide-Tris derivative has been synthesized and characterized using standard analytical and spectroscopic techniques including single crystal X-ray diffraction analyses. P1 exhibits interesting self-assembly behaviour leading to the generation of ~ 200 nm spherical aggregates in solutions as revealed by DLS and TEM analyses. Standard in vitro experiments revealed that P1 is capable of exhibiting moderate antioxidant properties under standard experimental conditions.A new [P2V3W15O62]9– cluster based covalent polyoxometalate-organic hybrid containing a naphthol-amide-Tris derivative has been synthesized and structurally characterized using single crystal XRD technique. The in vitro antioxidant activity and solution self-assembly properties of this hybrid are reported.Display Omitted
Keywords: Polyoxometalates; Organic–inorganic hybrid; Self-assembly; Crystal structure; Antioxidant activity;

A C 3-symmetrical yttrium complex [LY(THF)2] supported by a sterically encumbering N-anchored tris-arylphenoxide ligand was prepared by the reaction of H3L {L  = tris(4,6-di-tert-butyl-2-hydroxybenzyl)amine} and Y[N(TMS)2]3 in THF. The experimental results showed that this complex is a good catalyst for the heteroselective ring-opening polymerization (ROP) of rac-lactide, yielding polymers with Pr up to 0.73 under melt conditions at 130 °C. In addition, this complex [LY(THF)2] can effectively catalyze the coupling reaction of carbon dioxide with cyclohexene oxide using n-Bu4NCl/n-Bu4NBr/n-Bu4NI as a co-catalyst.A C 3-symmetrical yttrium complex [LY(THF)2] was prepared and the experimental results showed that this complex is a good catalyst for the heteroselective ring-opening polymerization (ROP) of rac-lactide, yielding polymers with Pr up to 0.73 under melt conditions at 130 °C. In addition, this complex [LY(THF)2] can effectively catalyze the coupling reaction of carbon dioxide with cyclohexene oxide using n-Bu4NCl/n-Bu4NBr/n-Bu4NI as a co-catalyst.Display Omitted
Keywords: Yttrium complex; rac-Lactide; Catalyst; Ring-opening polymerization; Cyclohexene oxide;

An unusual three-dimensional homochiral metal saccharate based on inorganic helical chains by Hua-Yi Zhang; Guang-Ju Zhang; Xin Wang; Juan Yang; Xiao-Lin Chi; Jin-Ling Zhang; Yu Chen; Qi Yang; Dong-Rong Xiao (73-75).
Self-assembly of the D-saccharate (D-sacc) ligand and barium salt under hydrothermal conditions yields an unprecedented homochiral three-dimensional (3D) metal saccharate, namely, [Ba(D-sacc)]n (1), which is based on inorganic helical chains as infinite rod-shaped secondary building units (SBUs). The structure of compound 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR spectrum, and thermogravimetric analysis. Compound 1 exhibits a novel 3D chiral architecture containing multidirectional helical chains, which is still rare in metal–organic complexes, especially in metal aldarates. To the best of our knowledge, compound 1 represents the first example of alkaline-earth metal aldarates featuring chiral and helical structures. Furthermore, the photoluminescent property of compound 1 was investigated in the solid state at room temperature.An unprecedented homochiral 3D metal saccharate, based on inorganic helical chains as infinite rod-shaped secondary building units, is reported, which represents the first example of homochiral alkaline-earth metal aldarates containing multidirectional helical chains.Display Omitted
Keywords: Metal saccharate; Chirality; Helicity; 3D architecture;

Highly selective CH2Cl2 fluorescent sensor based on Cd(II) metal-organic framework by Yan Xia; Ke-Li Cao; Min-Min Han; Yun-Long Feng (76-78).
Hydrothermal reaction of Cd2 + ions and 5-(4-carboxybenzyloxy)isoph-thalic acid (H3L) afforded a new 3D metal-organic framework (Cd-MOF), namely [Cd(HL)(2,2-bipy)] n ·1.25nH2O. The luminescent properties of Cd-MOF dispersed in different solvents have been investigated systematically, demonstrating unique selectivity for the detection of CH2Cl2 via a fluorescence quenching mechanism. The luminescent intensity of Cd-MOF was selectively quenched by Ni2 + ions.One new Cd(II) metal organic framework (Cd-MOF), namely [Cd(HL)(2,2-bipy)] n ·1.25nH2O was synthesized. The luminescent properties of the Cd-MOF dispersed in different solvents have been investigated systematically, demonstrating unique selectivity for the detection of CH2Cl2 via a fluorescence quenching mechanism. The luminescent intensity of Cd-MOF was selectively quenched by Ni2 + ions.Display Omitted
Keywords: 5-(4-Carboxybenzyloxy)isoph-thalic acid; Metal-organic framework; Luminescent properties;

Salen homonuclear and heteronuclear lanthanide(III) complexes with near-infrared (NIR) luminescence by Ruo-Xi Chen; Ting Gao; Wen-Bin Sun; Hong-Feng Li; Yu-Hong Wu; Miao-Miao Xu; Xiao-Yan Zou; Peng-Fei Yan (79-82).
Two lanthanide complexes are achieved by utilizing H2salen/acac ligands (H2salen =  N,N′-ethylenebis(salicylideneimine), acac = acetylacetonate). They are homonuclear [Nd4(μ 3-OH)2(salen)2(acac)6(CH3OH)2]·CH3OH (1) and heteronuclear [NdYb(salen)2(acac)2] (2). The structures of the two complexes were determined by X-ray crystallographic studies and their photophysical properties were investigated. The homonuclear Nd4 complex exhibits characteristic metal-centered NIR emission. The heteronuclear NdYb shows ‘dual emission’ from both neodymium(III) and ytterbium(III) ions.Two homonuclear and heteronuclear lanthanide complexes were constructed from salen and β-diketonate ligands. The homonuclear complex exhibits characteristic metal-centered NIR emission, while the heteronuclear complex shows ‘dual emission’.Display Omitted
Keywords: Salen; Homonuclear; Heteronuclear; Near-infrared (NIR);

Two luminescent bcu-type metal-organic frameworks constructed from distinct cadmium clusters by Ye-Yan Qin; Qing-Rong Ding; E Yang; Yao Kang; Lei Zhang; Yuan-Gen Yao (83-86).
Based on linear 1,4-benzeneditetrazol-5-yl ligand, two Cd(II) metal-organic frameworks have been constructed from square planar tetranuclear and linear trinuclear cadmium clusters, respectively, both of which show 8-connected bcu topology and luminescent properties.Two new 3D anionic 8-connected bcu-type metal-organic frameworks were synthesized and structurally characterized using polynuclear cadmium clusters as building units.Display Omitted
Keywords: MOFs; Cadmium clusters; Tetrazole; Topology; Photoluminescence;

The complexes Ir(III)(nbd2 2 −)(L-L)(acetylacetonate) with nbd2 2 −  = bis-norbornadienyl dianion and L-L = norbornadiene and 2,2′-bipyridyl and Pd(II)[C4(COOMe)4](2,2′-bipyridyl) contain metallacycles and a diolefin or bipyridyl as additional ligand. These complexes are characterized by low-energy LLCT excited states. The CT donor site is associated with the metallacycle while the CT acceptor function is provided by a diolefin or bipy. The LLCT triplets are emissive in solution under ambient conditions.Metallacycles such as metallacyclopentanes with Ir(III) and Pd(II) and a diolefin or bipy as additional ligand are characterized by low-energy (M-C σ-bond to π* of additional ligand) LLCT excited states. The corresponding LLCT triplets are luminescent under ambient conditions.Display Omitted
Keywords: Luminescence; Metallacycle; Iridium(III); Palladium(II); LLCT; Triplet emitter;

Synthetic methods, structural features, in situ rearrangement pattern and exciting properties of some model compounds are described in this short review.Syntheses involving in situ metal–ligand reactions, structural diversity and exciting properties of a set of novel coordination compounds along with probable reaction mechanisms of ligand rearrangement are outlined.Display Omitted
Keywords: Metal-ions; Polyamines; Rearrangements; Syntheses; Structures; Properties;

A novel 3D zinc metal–organic framework based on the tetrazole-containing ligand and tricarboxylic acid by Ze-Ping Wang; Mei-Ling Feng; Xing-Kun Xie; Xiao-Ying Huang (102-104).
A novel zinc metal–organic framework (MOF) with the combination of 5,5′-(1,4-phenylene)bis(1H-tetrazole) (H2BDT) and 1,3,5-benzenetricarboxylic acid (H3BTC) as the mixed ligands, namely [Me2NH2]4Zn2(BDT)(BTC)2 2DMF (1), has been solvothermally synthesized and characterized. Single-crystal X-ray analysis reveals that the structure of 1 features a pillared-layered three-dimensional (3D) anionic framework of [Zn2(BTC)2(BDT)] n 4n. The luminescent property studies indicated that 1 might be a potential blue-light material. It was found that the introduction of H3BTC could exhibit an obvious influence on the luminescence of 1, which can help us in better designing luminescent MOF materials.Presented is the first fluorescent Zn-MOF constructed from the mixed ligands of 5,5′-(1,4-phenylene)bis(1H-tetrazole) (BDT) and 1,3,5-benzenetricarboxylic acid (TDC).Display Omitted
Keywords: Metal–organic framework; Mixed ligands; Luminescence; Crystal structure; Pillared-layered framework;

The synthesis and structure of the first vanadium diperoxido complex carrying a monodentate amine ligand coordinated solely through its –NH2 group is reported herein. (S)-methylbenzylamine (mba) is acting as a ligand, while its protonated form is the cation in mbaH[VO(O2)2(mba)]∙H2O (1), which was isolated from a solution obtained by dissolving vanadium pentoxide in high excess of the amine and adding HCl and H2O2. [VO(O2)2(mba)] is the dominating species in this solution and shows a resonance at − 732 ppm in 51V NMR spectrum. The anion exhibits in infrared and Raman spectra bands typical for pentagonal pyramidal diperoxido complexes of vanadium. The band assignment of the characteristic vibrations was confirmed by DFT calculations.The first diperoxidovanadium complex with a monodentate amine ligand was synthesized and characterized by elemental analyses, IR and Raman spectroscopy, 51V NMR spectroscopy and X-ray structure analysis. High excess of (S)-methylbenzylamine and its protonated form allows formation and isolation of the title compound from aqueous solution.Display Omitted
Keywords: Vanadium peroxido complexes; Methylbenzylamine; 51V NMR spectroscopy; X-ray diffraction; DFT prediction;

A predesigned 1D chain of alternating di-μ1,1-azido bridged dinuclear Ni(II) and pyrazine: Synthesis, structure and magnetic properties by Rituparna Biswas; Soham Mukherjee; Soumavo Ghosh; Carmen Diaz; Ashutosh Ghosh (108-111).
A new Ni(II) complex, [Ni2(L)21,1-N3)2(pyz)]n (1) (where pyz = pyrazine) has been synthesized using a dinuclear di-μ1,1-azido bridged Ni2 molecular building block derived from a tridentate NNO donor Schiff base ligand, HL (2-[(3-methylamino-propylimino)-methyl]-phenol) along with pyrazine as spacer. Single crystal X-ray analysis shows that complex 1 is a 1D chain in which dimeric Ni2 units [Ni2L2(N3)2] are linked to each other by the bridging pyrazine ligand. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 53.54 cm− 1.A new ferromagnetic 1-D polynuclear chain of Ni(II) has been derived by joining dinuclear di-μ1,1-azido bridged nodes with pyrazine spacer.Display Omitted
Keywords: Ni2 molecular building block; Pyrazine spacer; 1-D chain; Ferromagnetic coupling;

Photocatalytic properties of two POM-templated organic–inorganic hybrid compounds by Xue-Jing Dui; Xiao-Yuan Wu; Jian-Zhen Liao; Teng Teng; Wei-Ming Wu; Wen-Bin Yang (112-115).
Reported are the rational synthesis, structures and properties of two novel organic–inorganic hybrid compounds, [Ag3(3-bpo)4(PMo12O40)]·~ 1.5H2O (1) and [Ag4(3-bpo)2(CH3CN)2(SiW12O40)] (2), where 3-bpo = 2,5-bis(3-pyridyl)-1,3,4-oxadiazole. Crystal structural analysis indicates that compound 1 exhibits one dimensional zigzag chains with the discrete [PMo12O40]3 − anions as guest molecules. While in compound 2 the POM anions as μ2-linkage bridging two chains construct supramolecular sheet. Both compounds were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. Furthermore, the excellent photocatalytic activity of compounds 12 was investigated under UV light irradiation.In hydrothermal conditions, two compounds [Ag3(3-bpo)4(PMo12O40)]·~ 1.5H2O (1) and [Ag4(3-bpo)2(CH3CN)2(SiW12O40)] (2) (3-bpo = 2,5-bis(3-pyridyl)-1,3,4-oxadiazole) were successfully synthesized. Crystal structural analysis indicates that compound 1 exhibits one dimensional zigzag chains with the discrete [PMo12O40]3 − anions as guest molecules. While in compound 2 the POM anions as μ2-linkage bridging two chains construct supramolecular sheet. Both compounds were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. Furthermore, the excellent photocatalytic activity of compounds 12 was investigated under UV light irradiation.Display Omitted
Keywords: Organic–inorganic hybrid compound; Polyoxometalates; Photocatalytic; Degradation;

A convenient method for the synthesis of Ru(II) pyridoxal thiosemicarbazone complex has been described. Elemental analysis, spectral methods and single crystal X-ray diffraction analysis were used to confirm the composition of the complex. The synthesized complex could act as an efficient, reusable homogeneous catalyst for transformation of aldehydes to the corresponding primary amides in the presence of NH2OH·HCl. The effect of solvent, base, temperature, time, catalyst loading and recyclability was also investigated.Ruthenium(II) thiosemicarbazone complex, [Ru(ONS)CO(PPh3)2], was synthesized and developed as an efficient catalyst for one-pot conversion of aldehydes to primary amide with a yield up to 91%.Display Omitted
Keywords: Ruthenium(II) TSC complex; Characterization; Crystal structure; One-pot synthesis of primary amide;

Reaction of 3-(2-pyridyl)pyrazole-5-carboxylic acid (H2L) with Zn(II) or Cu(II) perchlorate yielded [ZnL] n (1) and [CuL] n (2) with similar composition. The ligand L2 − adopts the same μ3κ5 coordination mode. The Zn(II) and Cu(II) atom takes square pyramid coordination polyhedron with some discrepancy. Bigger difference in the dimeric secondary building blocks leads to distinct two-dimensional metal–organic frameworks. The Zn(II) complex fluoresces stronger than the free ligand. The Cu(II) polymer displays strong antiferromagnetic intra-dimer exchange and ferromagnetic inter-dimer exchange.2D MOFs formed by 3-(2-pyridyl)pyrazole-5-carboxylate and Zn(II) or Cu(II) have similar compositions and coordination modes, but significant discrepancy in the dimeric secondary building blocks causes different coordination networks.Display Omitted
Keywords: Zinc; Copper; Pyrazolecarboxylic acid; Crystal structure; Luminescence; Magnetism;

Synthesis and characterization of novel coordination spin crossover poly(glycidyl methacrylate) with pendant iron(II)-4-amino-1,2,4-triazole groups by Wen-ping Wang; Zhi-qiang Zhang; Bi-bi Ji; Huai-hua Zhao; Guo-qing Li; Ling-xiang Ma; He-xiang Zhao (125-128).
Poly(glycidyl methacrylate) (PGMA) with pendant iron(II)-triazoles groups was synthesized through the grafting method. The structure was characterized by 1H NMR, FTIR and XRD. Meanwhile, SQUID and DSC were conducted to measure the spin crossover property of the composite. The Fe(II) complexes modified by PGMA not only display an evident spin crossover performance, but also have excellent processability.The Fe(II) complex modified by PGMA displays an evident spin crossover performance, according to the SQUID measurement and the color of complex in different temperatures.Display Omitted
Keywords: Spin crossover (SCO); PGMA; ATRP; Magnetic composite;

Construction of Zn(II)/Cd(II) coordination polymers derived from a tetrazole derivative: Syntheses, structures and luminescent properties by Jie Pan; Fei-Long Jiang; Ming-Yan Wu; Lian Chen; Xiu-Yan Wan; Yan Yang; Hui Xue; Mu-Xin Yu; Mao-Chun Hong (129-132).
Three new coordination polymers [Zn(Htip)Cl(H2O)]n (1), [Zn(Htip)2]n (2) and [Cd(Htip)2]n·2nH2O (3) were synthesized by reactions of Zn(II)/Cd(II) salts with a multidentate tetrazole-based ligand 2-(4-(tetrazol-5-yl)phenyl)imidazo(4,5-f)(1,10)phenanthroline (H2tip). Complex 1 possesses an infinite 1D coordination chain, and further forms the final 3D supramolecule through π⋯π stacking interactions. Complexes 2 and 3 are isomorphous, and both of them feature an 8-fold interpenetrating 4-connected 3D framework with the dia topological net and the Schläfli symbol of {66}. In 13, the Htip ligand links two metal centers through three terminal N-donors. The structural analyses indicate that the anions and solvents can subtly influence the formation of the resulting network. Moreover, the thermal stabilities and photoluminescent properties of 13 are investigated in the solid state.Three new Zn(II)/Cd(II) coordination polymers based on a multidentate tetrazole-containing ligand have been successfully synthesized. The structural analyses indicate that the anions and solvents can subtly influence the formation of the resulting network.Display Omitted
Keywords: Zn(II)/Cd(II) complexes; Tetrazole; Crystal structure; Interpenetration; Luminescence;

A new two-dimensional layered aluminophosphate [C9H14N]8[H2O]4·[Al8P12O48H4] (denoted as AlPO-CJ70) has been synthesized by using N,N-dimethylbenzylamine as the template under solvothermal conditions at 403 K. Single-crystal X-ray diffraction analysis reveals that the structure of AlPO-CJ70 consists of AAAA-stacked Al2P3O12 3 − layers made of alternating AlO4 and PO4 (PO3(=O) and PO2(=O)(OH)) tetrahedra, forming 1D 8-ring channels along the [100] direction. The inorganic layer exhibits a new type of 4 × 6 × 8 sheets with the Al/P ratio of 2/3. Protonated N,N-dimethylbenzylamine cations are located between the layers compensating the negative charge of the anionic framework. The existence of guest water and extensive H-bonds in the structure endows AlPO-CJ70 with proton conduction properties, as elucidated by impedance studies of the powder sample.A layered aluminophosphate AlPO-CJ70 constructed by a new type of 4 × 6 × 8 sheets with the stoichiometry of Al2P3O12 3 − was synthesized under solvothermal conditions, which shows interesting conduction properties when immersed in water.Display Omitted
Keywords: Aluminophosphate; Layered structure; Solvothermal synthesis; Proton conduction;

A luminescent europium metal–organic framework [Eu(HL)(L)(H2O)2]·2H2O (1) (H2L = (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid) with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu2 + in aqueous solution. To the best of our knowledge, complex 1 is the first luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites for selective sensing of Cu2 + in aqueous solution. The probable sensing mechanism was discussed in detail.A luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu2 + in aqueous solution.Display Omitted
Keywords: Europium metal–organic framework; Luminescence; Sensor; Phenanthroline; Cu2 +;

Corrigendum to “Fac-tricarbonyl(pentylcarbonato)(α-diimine)rhenium complexes: One-pot synthesis, characterization, fluorescence studies, and cytotoxic activity against human MDA-MB-231 breast, CCl-227 colon and BxPC-3 pancreatic carcinoma cell lines” [Inorg. Chem. Commun. 21 (2012) 35–38] by Michael K. Mbagu; Divine N. Kebulu; Angela Winstead; Saroj K. Pramanik; Hirendra N. Banerjee; Maurice O. Iwunze; James M. Wachira; George E. Greco; Gregory K. Haynes; Amanda Sehmer; Fazlul H. Sarkar; Douglas M. Ho; Robert D. Pike; Santosh K. Mandal (141).