Inorganic Chemistry Communications (v.59, #C)

Contents List (iii-ix).

Three discrete and elongated Wells–Dawson type clusters [Ln24(DMC)364-CO3)183-H2O)2]·nH2O (Ln = Tb (1), n = 4.5; Ln = Ho (2), n = 6; Ln = Er (3), n = 9; DMC = N, N-dimethylcarbamic acid anions) were synthesized by solvothermal. The ligands DMC and CO3 2 − derived from the oxide reaction of DMF in situ. The metal skeleton of the cluster can be ascribed as an elongated Wells–Dawson type polyoxometalate (POM) polyhedron comprised of eighteen Ln44-CO3) square units and two Ln33-H2O) triangles. The magnetic properties of three clusters were explored, and all of them did not exhibit frequency-dependence. The compound 1 shows the typical luminescence of Tb3 +. Interestingly, water molecules can significantly decrease the luminescent intensity, and other organic solvents including nitrobenzene have almost no effect on emission.Three discrete and elongated Wells–Dawson type Ln24 (Ln = Tb, Ho and Er) clusters were synthesized by solvothermal, and the magnetic and luminescent properties were explored.Display Omitted
Keywords: Lanthanide clusters; Magnetic property; Luminescence; Wells–Dawson type;

A new compound based on capped polyoxometalates (POMs), [Ag(phen)2]2(Agphen)2SiW12O40 (phen = 1,10-phenanthroline), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, infrared spectrum, UV–vis electronic spectrum, elemental analyses, and powder X-ray diffraction pattern. The structural feature of compound 1 is that each [SiW12O40]4 − (SiW12) cluster capped by two (Agphen)+ fragments. To the best of our knowledge, the compound 1 represents the first example of hybrid compound based on bi-silver-capped POMs to date. The photocatalytic properties of compound 1 were also investigated in detail and the results of photocatalytic experiment show that compound 1 can be used as a photocatalyst towards the decomposition of organic pollutant methylene blue (MB).A hybrid compound consisting of an unprecedented bi-silver-capped polyoxometalates has been hydrothermally synthesized, and its photodecomposition behavior towards methylene blue has been investigated.Display Omitted
Keywords: Bi-silver-capped polyoxometalate; Photocatalytic property; Keggin;

Two CdII coordination polymers, namely {[Cd(L434)(Br)(N3)](H2O)1.75} n (1) and [Cd(L434)(I)(N3)(H2O)] n (2) (L434  = 3,5-bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole) have been synthesized by reaction of L434 with CdBr2 or CdI2 in the presence of NaN3 under the same conditions. Single-crystal X-ray diffraction analyses indicate that complex 1 shows a 3D coordination network with unusual gra topology, whereas 2 has a 1D ladder-like coordination chain. The structural distinction on the two complexes, including the different coordination environments of CdII and binding modes of L434 and N3 , can be ascribed to the usage of different halide anions from Br to I. In addition, the solid-state properties for complexes 1 and 2 such as thermal stability and fluorescence properties have also been investigated.Two CdII coordination polymers, namely {[Cd(L434)(Br)(N3)](H2O)1.75} n (1) and [Cd(L434)(I)(N3)(H2O)] n (2) (L434  = 3,5-bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole) have been synthesized by reaction of L434 with CdBr2 or CdI2 in the presence of NaN3 under the same conditions. Complex 1 shows a 3D coordination network with unusual gra topology, whereas 2 has a 1D ladder-like coordination chain. The structural distinction on the two complexes, including the different coordination environments of CdII and binding modes of L434 and N3 , can be ascribed to the usage of different halide anions from Br to I.Display Omitted
Keywords: 3,5-Bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole; Halide anions; Coordination polymers; CdII complexes;

A new tetraphenylporphyrin-tungstophosphoric acid hybrid was synthesized and physico-chemically characterized by different techniques. This hybrid, its molybdenum analogue, tungstophosphoric and molybdophosphoric acids as well as their Mn, Fe and Co salts were applied in Baeyer–Villiger oxidation of cyclohexanone to caprolactone with molecular oxygen. Due to the synergistic effect porphyrin-heteropolyacid hybrids exhibit similar catalytic activity as appropriate heteropoly salts and much higher activity than parent heteropolyacids.New tetraphenylporphyrin-tangstophosphoric heteropolyacid hybrid was synthesized and applied as catalyst in oxidation of cyclohexanone to caprolactone showing synergistic effect.Display Omitted
Keywords: Organic-inorganic hybrid; Poyoxometalate; Porphyrin; Cyclohexanone oxidation;

A novel lead borate of NaPb4(H2O)(B5O9)2·BO3 with nonlinear optical property by Guang Huang; Rui Pan; Huan He; Bai-Feng Yang; Guo-Yu Yang (17-20).
A new mixed metal borate, NaPb4(H2O)(B5O9)2·BO3, with an acentric structure has been successfully made under hydrothermal conditions and structurally characterized by IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction, respectively. The structural analysis shows that 1 crystallizes in the orthorhombic space group Pnn2 (No. 34) with a  = 11.3724(5) Å, b  = 11.4455(4) Å, c  = 6.5578(2) Å and Z  = 2. In the structure 1, the structural building unit, B5O12 cluster, connects adjacent six same ones to form a 3-D oxoboron framework with 8-membered ring (MR) and 10-MR channels along the c-axis. The Pb atoms and coordinated water molecules are located in the 8-MR channels, while the 10-MR channels were occupied by the chains built by Na atoms and the BO3 groups. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits SHG efficiency approximately 2 times that of KH2PO4 (KDP). Also it has a UV cutoff edge below 220 nm.A novel acentric lead borate, NaPb4(H2O)(B5O9)2·BO3 has been hydrothermally made, in which the 3-D oxoboron framework with 8-membered ring (MR) and 9- and 10-MR channels is built by B5O12 cluster units, showing the second-harmonic generation efficiency approximately 2 times that of KH2PO4 (KDP), and its UV cutoff edge below 220 nm.Display Omitted
Keywords: Borate; Cluster; Nonlinear optical; Hydrothermal syntheses; Crystal structure;

Three novel lanthanide polymers, [Ln(III)(L)3EtOH]n (Ln = Tb(1), Ho(2), Er(3), HL = 2,3,5-trichlorobenzoic acid), have been solvothermal synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy and element analyses. The three polymers crystallize in triclinic space group P-1. The Ln(III) ions are in turn bridged by double and quadruple carboxylate of L ligands to form one-dimensional (1D) chains. Magnetic studies reveal that polymer 1 demonstrates dominant ferromagnetic behavior, polymer 2 shows antiferromagnetic behavior, and polymer 3 present spin-canting behavior.Three novel lanthanide polymers based on 2,3,5-trichlorobenzoic acid have been solvothermal synthesized and characterized. Polymers 1–3 are isostructural which crystallize in the triclinic space group P-1. Magnetic studies reveal that polymer 1 demonstrates dominant ferromagnetic behavior, polymer 2 shows antiferromagnetic behavior, and polymer 3 presents spin-canting behavior.Display Omitted
Keywords: Crystal structure; Lanthanide polymers; Solvothermal synthesis; Magnetic properties;

The reaction of uranyl nitrate with 3-(pyrimidin-2-yl)benzoic acid (LH) in the presence of nickel(II) nitrate and 1,10-phenanthroline (phen) yields the complex [Ni(phen)3][UO2(L)3]2·2.5H2O (1), in which the uranium atom is chelated by three carboxylate groups. Analysis of short intermolecular contacts shows that those associated with π⋯π interactions do not show up prominently, notwithstanding the number of aromatic rings present, and the packing mode appears to be primarily a result of Coulombic interactions and best shape fitting.Notwithstanding the large number of aromatic rings present in the uranyl ion complex of 3-(pyrimidin-2-yl)benzoic acid with Ni(phen)3 2 + counter-ions, π⋯π interactions appear to be of little importance in the packing, which is governed by Coulombic interactions and displays an intricate interlocking of cations and anions.Display Omitted
Keywords: Uranyl; Aromatic interactions; Structure elucidation; Hirshfeld surfaces;

Two complexes based on the 5-hydroxy-pyridine-2-carboxylic acid (H2L), namely, [Cd(HL)2(H2O)2]n, (1), and [Cd(L)(H2O)]n (2) were characterized by the elemental analysis, infrared spectra, thermogravimetric analysis, and single crystal X-ray diffractions. The structural analyses revealed that complex 1 is a discrete mononuclear unit, which are extended to form 3D supramolecular architectures by hydrogen bonds. Compound 2 is a three dimensional network with a topological Schläfli symbol of {42.63.8}. By adjusting the pH of reaction system, the results indicate that reacting pH plays a vital role in the assembly process of structural transition. The thermal stability and solid-state photoluminescence of compounds 12 were further explored.A transition from 0D to 3D assembly of supramolecular architectures has occurred. The results reveal that reaction pH plays a vital role in the assembly process of structural transition of compounds 12. The photoluminescent properties of 12 were further investigated.Display Omitted
Keywords: Coordination compounds; pH-dependence; Crystal structures; Photoluminescence;

A fascinating 3D pillared-layer structure, namely [Cd3(bpea)2(trz)2(H2O)2]·DMF (1), has been isolated under hydrothermal condition by reaction of cadmium salt, biphenylethene-4,4′-dicarboxylic acid (bpea) and 1,2,4-triazole (Htrz). Compound 1 presents an unusual self-penetrating network displaying uninodal seven-connected {414·5·66} topology with trinuclear cadmium clusters as seven-connected nodes, which exhibited exceptional resistance to acid/base aqueous solutions. Furthermore, solvent-dependent luminescence properties of 1 were investigated, and the results showed that 1 could serve as a potential luminescent sensor in detecting traces of the target species, such as toluene and nitrobenzene.A pillared-layer MOF defines an unprecedented self-penetrating topology for seven-connected networks, and exhibits excellent solvent-dependent luminescence properties.Display Omitted
Keywords: Metal-organic framework; Self-penetrating network; Stability; Luminescent probe;

Two new complexes formed by uranyl ions with succinic acid and 4,4′-dipyridine have been investigated. Interestingly, the uranium(VI) coordination polymers possess two types dioxido unit, a cis-dioxido bond angle with 115.421(2)°and a trans-dioxido bond angle with 178.421(2)°, respectively. The complexes were characterized by elemental analysis, IR and UV–vis spectroscopy and X-ray crystal diffraction. In addition, the properties of luminescence and photocatalytic analysis were also investigated. The result revealed that the two complexes show different photocatalytic activity in the decomposition of RhB under visible light and UV light irradiation.The details process of reactions, the coordination environment and the UV–vis absorption spectra of the RhB solution during the decomposition reaction for complex 1.Display Omitted
Keywords: cis-Dioxido; Uranyl; Carboxylate; Crystal;

In this paper, the Zn-based analogue of Cu3(btc)2 (HKUST-1), Zn3(btc)2 nanorods (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) have been synthesized through direct precipitation in solution phase under ultrasound condition without the assistance of any surfactant, catalyst, or template. Zn-HKUST-1 nanorods werecharacterized by Fourier transform infrared studies, elemental analysis, powder X-ray diffraction and field emission scanning electron microscopy. Concentration of initial reagent effects on size and morphology of the Zn-HKUST-1 has been studied and shows that low concentrations of initial reagents decreased widths, thicknesses, and lengths of nanorods. Subsequently, ligand-free ZnO nanorods and nanoparticles are selectively prepared via a thermal decomposition method using the corresponding nanorods and single crystals as a precursor, respectively. This solid-state transformation route is promising for the preparation of crystalline nanomaterials with desired morphologies because of its simplicity and the low cost of the starting reagents.Zn-based analogue of Cu3(btc)2 (HKUST-1), Zn3(btc)2 nanorods (Zn-HKUST-1) have been synthesized through direct precipitation in solution phase under ultrasound condition. Subsequently, ligand-free ZnO nanorods and nanoparticles are selectively prepared via a thermal decomposition method using the corresponding nanorods and single crystal framework as a precursor, respectively.Display Omitted
Keywords: Ultrasound; Metal–organic framework; Nanorod; Zinc oxide;

A mononuclear copper(II) complex [Cu(dipica)(CH3COO)]ClO4 (1), where dipica is di-(2-picolyl)amine, has been isolated. The electronic absorption (646 nm) and electron paramagnetic resonance (EPR) spectral parameters (g||, 2.223; A||, 187 × 10− 4  cm− 1; g||/A||, 119 cm) reveal that 1 possesses a near square planar geometry with CuN3O chromophore. Absorption, circular dichroic and emission spectral measurements and electrochemical measurements clearly demonstrate groove binding of 1 to calf thymus DNA. Notably, 1 exhibits more effective DNA (pUC 19 DNA) cleavage at acidic pH. It shows significant cytotoxicity (IC50, 55 μM) against human cervical carcinoma cells (HeLa) at 48 h incubation time and is non-toxic to healthy cells.The water soluble copper(II) complex is involved in groove binding with CT DNA. It shows a profound efficiency to cleave plasmid DNA at acidic pH. It is cytotoxic to HeLa cancer cells whereas it is non-toxic to normal cells.Display Omitted

A new molybdovanadate, (NH4)12[Na(H2O)5][Na(H2O)2]2[Fe5CoMo22V2O87(H2O)]·19H2O (1) was synthesized and structurally characterized by elemental analysis, IR spectra, UV electronic spectroscopy and X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) pure inorganic chain-like framework based on banana-shaped molybdovanadate anions [Fe5CoMo22V2O87(H2O)]15 −. Further, compound 1 exhibits good electrocatalytic activity for nitrite reduction. The magnetic investigation reveals a distinct occurrence of ferromagnetic interactions among its Fe5Co cluster.A novel molybdovanadate consisting of banana-shaped molybdovanadate [Fe5CoMo22V2O87(H2O)]15 − anions arise from a pH-dependent self-assembly process, in which {[Na(H2O)5][Fe5CoMo22V2O87(H2O)]}14 − anions could be bridged by [Na2O10] unit to form the 1D helical chain framework.Display Omitted
Keywords: Molybdovanadate; 1D helical chain; Electrocatalysis; Magnetic property;

Lanthanide complexes with a biphosphonate ester ligand and their fluorescent properties by Linyue Zhang; Wei Dou; Wei Liu; Cong Xu; Huie Jiang; Chunyang Chen; Lirong Guo; Xiaoliang Tang; Weisheng Liu (53-56).
A bi-phosphonate ligand 4,4′-bis(diethylphosphonomethyl)biphenyl has been designed and synthesized. The ligand reacted with lanthanide nitrates forming three different types of coordination complexes: interwoven net polymer (type I), linear polymer (type II), and ladder polymer (type III). The photophysical properties of Sm3 +, Eu3 +, Tb3 + and Dy3 + complexes were investigated. The Sm3 +, Eu3 + and Dy3 + complexes displayed the characteristic spectrum of the lanthanide ions. The Tb3 + complex exhibited a prominent strong fluorescence by excitation of 300 nm, which indicated that there may be a luminescence sensitization effect of the complex via excitation of the ligand.Lanthanide complexes with a bi-phosphonate ligand of three different coordination networks (zigzag chain interwoven, linear and ladder) have been synthesized. Their luminescence properties were also investigated.Display Omitted
Keywords: Phosphonate ligand; Coordination polymers; Crystal structure; Lanthanide fluorescence;

The “periodic table” of benzotriazoles: Uranium(VI) complexes by Sokratis T. Tsantis; Maria Mouzakitis; Aikaterini Savvidou; Catherine P. Raptopoulou; Vassilis Psycharis; Spyros P. Perlepes (57-60).
The first employment of benzotriazoles in uranium(VI) chemistry has led to uranyl complexes with interesting structures and spectroscopic properties; the reactions of uranyl nitrate with 5,6-dimethylbenzotriazole give two products depending on the reactants' molar ratio.The first employment of simple benzotriazoles in U(VI) chemistry gives mononuclear uranyl complexes with interesting structural and spectroscopic features.Display Omitted
Keywords: Benzotriazoles; Crystal structures; Raman spectra; Uranyl complexes;

Through the self-assembly of the typical Salen-type Schiff-base ligand H2L (H2L  = N,N′-bis(salicylidene)cyclohexane-1,2-diamine) and an excess of Zn(OAc)2·2H2O in the presence of Et3N, a new tetranuclear complex [Zn4(L)2(OAc)3(OH)] (1) with multiple active species and self-owned normal initiators was obtained and shown to efficiently catalyze the bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide, giving the uniformly isotactic poly-l-lactides (PLLAs).A new tetranuclear complex [Zn4(L)2(OAc)3(OH)] (1) with multiple active species and self-owned normal initiators was shown to efficiently catalyze the bulk solvent-free melt ROP of l-lactide, giving the uniformly isotactic PLLAs.Display Omitted
Keywords: Tetranuclear Zn2 + Schiff-base complex; ROP from l-lactide; Bulk solvent-free melt procedure; Isotactic PLLA;

Effect of Eu3 + concentration on the photocatalytic activity of LaSr2AlO5 powders by C.R. García; L.A. Diaz-Torres; Jorge Oliva; M.T. Romero; G.A. Hirata (63-67).
The photocatalytic activity of LaSr2AlO5:Eu3 + (LSA:Eu) ceramic powders was studied by monitoring the degradation of methylene blue (MB) dye in water under UV excitation (253 nm). Several LSA:Eu samples were fabricated with Eu3 + concentrations from 1 to 10 at.%. XRD patterns show a single tetragonal phase for all LSA:Eu samples. Scanning electron micrographs of the ceramic powders depicted coalesced particles with average sizes in the range of 3.5–4.27 μm. The optical bandgap of these powders varies between 4.7 eV and 5.1 eV depending on the Eu3 + concentration. The results of photocatalytic activity indicate that MB degradation rate increases as the Eu content increases. In fact, total MB degradation is reached after 360 min under UV light by using LSA:Eu (10 at.%) powders, and these can be removed easily after photocatalytic water treatment. Thus, LSA:Eu powders could be potential photocatalyst for water cleaning applications.a) Unit-cell schematic representation of LaSr2AlO5:Eu3 +. The spheres represent the following atoms: La/Eu (purple), Sr (green), Al (yellow) and O (red). b) LaO8 coordination formed by the La atom and the O atoms which is similar to the Eu and O atoms' coordination EuO8. c) Integrated absorbance bar graph of methylene blue solution catalyzed with LSA:Eu (10 at.%) photocatalyst powder as a function of time. The inset shows photographs of the solution with MB at the beginning (0 min) and at the end of the experiment (360 min).Display Omitted
Keywords: Photocatalysis; Luminescence; Europium; Lanthanum; Ultraviolet; Methylene blue;

One diethylamine coumarin derivative with nitro substituted chalcone structure as chemosensor for cyanide and copper ions by Yanyan Shan; Yunhui Sun; Ning Sun; Ruifang Guan; Duxia Cao; Kangnan Wang; Qianqian Wu; Yongxiao Xu (68-70).
One diethylamine coumarin derivative with nitro substituted chalcone structure was synthesized via typical condensation reaction between 4-nitro-2-(hydroxyl)acetophenone with 7-(diethylamino)coumarinaldehyde in good yields. The investigation indicated that the compound exhibits quickly obvious UV–vis absorption, color change and fluorescence response to cyanide and copper ions in acetonitrile conditions. The bonding mechanism based on spectra change and in situ 1H NMR suggested that cyanide is bonded to 4-position of coumarin and 1:2 complexation between compound and copper ion forms.One diethylamine coumarin derivative with nitro substituted chalcone structure was synthesizes, which can recognize cyanide and copper ions with quickly obvious UV–vis absorption, color change and fluorescence turn-off response.Display Omitted
Keywords: Coumarin derivative; Chalcone; Copper ion; Cyanide anion; Chemosensor;

Synthesis, structural studies, and oxidation catalysis of the manganese(II), iron(II), and copper(II) complexes of a 2-pyridylmethyl pendant armed side-bridged cyclam by Anthony D. Shircliff; Kevin R. Wilson; Desiray J. Cannon-Smith; Donald G. Jones; Zhan Zhang; Zhuqi Chen; Guochuan Yin; Timothy J. Prior; Timothy J. Hubin (71-75).
The first 2-pyridylmethyl pendant armed structurally reinforced cyclam ligand has been synthesized and successfully complexed to Mn2 +, Fe2 +, and Cu2 + cations. X-ray crystal structures were obtained for the diprotonated ligand and its Cu2 + complex demonstrating pentadentate binding of the ligand with trans-II configuration of the side-bridged cyclam ring, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of these complexes were determined by means of solid state magnetic moment, with a low value of μ = 3.10 μB for the Fe2 + complex suggesting that it has a trigonal bipyramidal coordination geometry, matching the crystal structure of the Cu2 + complex, while the μ = 5.52 μB value for the Mn2 + complex suggests that it is high spin octahedral. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all three complexes, suggesting that catalytic reactivity involving electron transfer processes are possible for these complexes. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant identified the Fe2 + complex as the oxidation catalysts most worthy of continued development.2-Pyridylmethyl pendant armed ethylene side-bridged cyclam complexes of copper(II), iron(II), and manganese(II) have been prepared, characterized, and screened for oxidation catalysis.Display Omitted
Keywords: Structurally reinforced cyclam; Side-bridged cyclam; Pendant-arm macrocycle; Oxidation catalysis; 2-Pyridylmethyl;

Complexes of 2,6-diacetylpyridine dihydrazone with middle and late first row transition metals by Allen J. Osinski; Bradley A. Hough; Laura A. Crandall; Ingrid-Suzy Tamgho; Christopher J. Ziegler (76-79).
A study of the transition metal chemistry with the planar tridentate ligand 2,6-diacetylpyridine dihydrazone (1, DAPH) is presented, expanding the chemistry of this ligand across the first row of the transition metals. Ligand 1 forms both 1:1 and homoleptic 2:1 complexes with transition metal ions, depending on the metal salt used and reaction conditions, and seven new complexes with Mn, Fe, Co, Cu and Zn are presented. All compounds, including the ligand, have been characterized by X-ray crystallography. DAPH (1) binds to metal ions in an asymmetric fashion, with a M–Npyr bond that is shorter than the flanking M–Nimine bonds. Additionally, the Nimine–M–Nimine bonds form acute angles ranging from ~ 140 to 160°, depending on the identity of the metal ion and ligand environment. All compounds are compared with previously elucidated DAPH structures from the literature.Display Omitted
Keywords: 2,6-Diacetylpyridine dihydrazone; Transition metal complexes; X-ray crystallography; Homoleptic complexes;

Non-photochemical synthesis of Re(diimine)(CO)2(L)Cl (L = phosphine or phosphite) compounds by Daniel A. Kurtz; Badrinath Dhakal; Elizabeth S. Donovan; Gary S. Nichol; Greg A.N. Felton (80-83).
The synthesis and characterization of a series of compounds of the type Re(diimine)(CO)2(L)Cl (where L = P(OEt)3, PMe3) is reported. The non-photochemical ligand substitution (non-PLS) utilizes the trans-labilizing effect of phosphorus ligands to facilitate carbonyl replacement. The non-PLS pathway leads to good yields (> 60%) of single isomer products, comparing favorably to the lower yield, mixed isomer products of analogous PLS pathways. The substitution of a carbonyl group by a phosphine/phosphite ligands shifts absorption further into the visible region without diminishing molar absorptivity. The synthesis presented provides a general facile ligand substitution pathway for related light-sensitive neutral rhenium/manganese carbonyl halide compounds.A generalized reaction is shown for the primary products of the paper. A light bulb is crossed-out to indicate that the synthesis is non-photochemical in nature. Below this are sample UV/vis spectra (highlighting the bathochromic shift upon ligand substitution).Display Omitted
Keywords: Rhenium; UV/vis spectroscopy; Bipyridine; Electrochemistry; Metal-carbonyl;

Anhydrous manganese hypophosphite dense framework solid: Synthesis, structure and magnetic studies by Gulzar A. Bhat; Pratap Vishnoi; Sandeep K. Gupta; Ramaswamy Murugavel (84-87).
Anhydrous manganese hypophosphite, [Mn(H2PO2)2] n ·(DMF)0.11 (1) has been isolated under solvothermal conditions from the reaction of hypophosphorous acid (H3PO2) and MnCl2·4H2O in a mixture of DMF/EtOH/H2O (8:1:1; v/v) in 60% yield. The compound is characterized by FT-IR spectroscopy, thermogravimetric analysis, PXRD, single crystal X-ray diffraction data and magnetic measurements. The ligand occupies all the octahedral coordination sites around Mn(II) ions and forms a dense 3-D coordination polymer with hexagonal 1-D channels along [001] direction. The Mn(II) ions in the framework exhibit weak antiferromagnetic interactions.Anhydrous Mn(II)-hypophosphite 3-D framework with 1-D channels has been synthesised and structurally characterized. Thermolysis of the framework leads to the formation of stable Mn2P2O7. Mn(II) centres exhibit weak antiferromagnetic interactions.Display Omitted
Keywords: Anhydrous manganese hypophosphite; Solvothermal synthesis; 3-D network; 1-D channel; Antiferromagnetic coupling;

Synthesis, characterization, and pepsin inhibition study of Au(III)–3-(2′-thiazolylazo)-2,6-diaminopyridine complex by Akkharadet Piyasaengthong; Nonlawat Boonyalai; Songwut Suramitr; Apisit Songsasen (88-90).
Complex between Au(III) and 3-(2′-thiazolylazo)-2,6-diaminopyridine (TADAP) was synthesized, characterized and found to inhibit pepsin activities at the concentrations between 0–200 μM. The IC50 value of the complex toward pepsin was 9.45 μM. Our kinetic study suggested that Au(III)–TADAP complex could act as the uncompetitive inhibitor. These findings have provided the first information of Au(III)–TADAP complex as a protease inhibitor.Display Omitted
Keywords: Au(III) complex; 3-(2′-Thiazolylazo)-2,6-diaminopyridine; Pepsin inhibition;

Three rare earth–nitronyl nitroxide radical complexes [Ln(hfac)3(NIT-1′-MeBzIm)] (Ln(III) = Gd 1, Tb 2, Dy 3; hfac = hexafluoroacetylacetonate; NIT-1′-MeBzIm = 2-{2′-[(l′-methyl)-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been successfully prepared and structurally characterized. X-ray crystallographic analysis reveals that all the three complexes are isomorphous. The center lanthanide(III) ions are eight-coordinated to one NIT-1′-MeBzIm and three hexafluoroacetylacetonate ligands. The NIT-1′-MeBzIm acts as a bidentate ligand via its nitrogen atom of the imidazole ring and the oxygen atom of the N–O group. The magnetic properties of complexes 1, 2 and 3 were studied. All of them exhibit ferromagnetic interaction. AC magnetic susceptibility studies show that Tb complex displays frequency-dependent signals at low temperature suggesting that it behaves as SMM.Three new lanthanide–radical complexes have been successfully prepared. The magnetic studies reveal that Tb complex shows the presence of frequency-dependent signals at low temperature suggesting that it behaves as SMM.Display Omitted
Keywords: Nitronyl nitroxide; Lanthanides; Crystal structure; Magnetic properties;

A new polyborate anion, [B7O9(OH)6]3−: Self assembly, XRD and thermal properties of s-fac-[Co(dien)2][B7O9(OH)6]·9H2O by Mohammed A. Altahan; Michael A. Beckett; Simon J. Coles; Peter N. Horton (95-98).
The title compound, s-fac-[Co(dien)2][B7O9(OH)6]·9H2O (1) (dien = HN(CH2CH2NH2)2), has been prepared as a crystalline solid in moderate yield (35%) from the reaction of B(OH)3 with [Co(dien)2][OH]3 in aqueous solution (10:1 ratio). The structure contains a novel polyborate anion [B7O9(OH)6]3 − which is structurally based on the known ‘ribbon’ isomer of [B7O9(OH)5]2 −, with an additional [OH] group coordinated to a B atom in one of the outer boroxole rings. Compound 1 is formed by a self-assembly process in which the cation and anion mutually template themselves from equilibrium mixtures under reaction conditions. The [B7O9(OH)6]3 − anions are H-bonded to each other in layers with ‘cavities’ suitable for the [Co(dien]2]3 + complex. Three [B7O9(OH)6]3 − anions are in the secondary coordination sphere (via H-bonds) of each cation, with each anion H-bonded to three cations. s-fac-[Co(dien)2][B7O9(OH)6]·9H2O (1) contains a novel isolated heptaborate anion [B7O9(OH)6]3 −. 1 is formed by a self-assembly process in which the cation and anion mutually template themselves from equilibrium mixtures under reaction conditions. The heptaborate(3-) anion has 3 boroxole (B3O3) rings linked by spiro B centres, and an additional 4 coordinate B atom.Display Omitted
Keywords: [B7O9(OH)6]3 −; Heptaborate(3-); s-fac-[Co(dien)]3 +; Self-assembly; XRD structure;