Volume 68, Issue 9

The rare-earth fluoride borate LaB 2 O 4 F was synthesized under high-pressure=high-temperature conditions of 1.1 GPa and 1300 °C in a Walker-type multianvil apparatus from lanthanum oxide, lanthanum fluoride, and boron oxide. The single-crystal structure determination revealed that LaB 2 O 4 F is isotypic to CeB 2 O 4 F. The compound crystallizes in the orthorhombic space group Pbca (no. 61) with eight formula units and the lattice parameters a = 8.2493(9), b = 12.6464(6), c = 7.3301(5) Å , V = 764.7(2) Å3, R 1 = 0.0354, and wR 2 = 0.0474 (all data). The structure exhibits a 9+1 coordinated lanthanum cation, one threefold coordinated fluoride ion and a chain of corner-sharing [BO 3 ] 3- groups. In addition to the IR- and Raman-spectroscopic investigations, DFT calculations were performed to support the assignment of the vibrational bands Graphical Abstract High-pressure Synthesis and Characterization of the Rare-earth Fluoride Borate LaB 2 O 4 F

The solid solutions Ce(Rh 1 - x Ru x )Sn were investigated by means of susceptibility measurements, specific heat, electrical resistivity, X-ray absorption spectroscopy (XAS), and 119 Sn Mössbauer spectroscopy. Magnetic measurements as well as XAS data show a cerium valence change in dependence on the ruthenium content. Higher ruthenium content causes an increase from 3.22 to 3.45 at 300 K. Furthermore χ and χ -1 data indicate valence fluctuation for cerium as a function of temperature. For example, Ce(Rh 0:8 Ru 0:2 )Sn exhibits valence fluctuations between 3.42 and 3.32 in the temperature range of 10 to 300 K. This could be proven by using the interconfiguration fluctuation (ICF) model introduced by Sales and Wohlleben. Cerium valence change does not influence the tin atoms as proven by 119 Sn Mössbauer spectroscopy, but it influences the electrical properties. Ce(Rh 0:9 Ru 0:1 )Sn behaves like a typical valence fluctuating compound, and higher ruthenium content causes an increase of the metallic behavior Graphical Abstract Cerium Valence Change in the Solid Solutions Ce(Rh 1-x Rux)Sn

The ternary antimonides RE 4 T 7 Sb 6 (RE=Gd-Lu; T =Ru, Rh) have been synthesized from the elements by arc-melting and subsequent annealing in an induction furnace. The samples have been characterized by powder X-ray diffraction. Four structures were refined on the basis of single-crystal X-ray diffractometer data: U 4 Re 7 Si 6 type, space group Im3m with a=862.9(2) pm, wR2=0.0296, 163 F 2 values for Er 4 Ru 7 Sb 6 ; a=864.1(1) pm, wR2=0.1423, 153 F 2 values for Yb 4 Ru 7 Sb 6 ; a=872.0(2) pm, wR2=0.0427, 172 F 2 values for Tb 4 Rh 7 Sb 6 ; and a=868.0(2) pm, wR2=0.0529, 154 F 2 values for Er 4 Rh 7 Sb 6 , with 10 variables per refinement. The structures have T1@Sb 6 octahedra and slightly distorted RE@T2 6 Sb 6 cuboctahedra as building units. The distorted cuboctahedra are condensed via all trapezoidal faces, and this network leaves octahedral voids for the T1 atoms. The ruthenium-based series of compounds was studied by temperature-dependent magnetic susceptibility measurements. Lu 4 Ru 7 Sb 6 is Pauli-paramagnetic. The antimonides RE 4 Ru 7 Sb 6 with RE=Dy, Ho, Er, and Tm show Curie-Weiss paramagnetism. Antiferromagnetic ordering occurs at 10.0(5), 5.1(5) and 4.0(5) K for Dy 4 Ru 7 Sb 6 , Ho 4 Ru 7 Sb 6 and Er 4 Ru 7 Sb 6 , respectively, while Tm 4 Ru 7 Sb 6 remains paramagnetic. Yb 4 Ru 7 Sb 6 is an intermediate-valent compound with a reduced magnetic moment of 3.71(1) μ B per Yb as compared to 4.54 μ B for a free Yb 3+ ion Graphical Abstract Ternary Antimonides RE 4 T 7 Sb 6 (RE=Gd–Lu; T =Ru, Rh) with Cubic U 4 Re 7 Si 6 -type Structure

Herein we report on the syntheses, crystal structures and first electrochemical characterizations of ternary zirconium transition metal (poly)antimonides Zr 2 TSb 3 (with T = Cu, Pd) and Zr 3 TSb 7 (with T = Ni, Pd). The compounds were synthesized by arc-melting, followed by an annealing procedure at elevated temperatures. Phase analysis and structure analysis were performed by powder and singlecrystal measurements. The electrochemical properties of all compounds were measured in half cells against lithium to test their potential as anode materials for Li batteries. The Zr 3 TSb 7 phases show metallic behavior with conductivities of 10 -1 S cm -1 within a temperature range of 324 to 428 K Graphical Abstract Zirconium Transition Metal (Poly)antimonides – Syntheses, Characterization and Electrochemical Properties

A polyoxometalate-based copper(II) inorganic-organic hybrid polymer [Cu(dpdo) 2 (H 2 O) 4 ] [Na 2 (Mo 8 O 26 ) (H 2 O) 6 ] (dpdo) 2H 2 O (1) (dpdo=4,4’-bipyridine-N,N'-dioxide) has been synthesized and structurally characterized by IR spectroscopy, elemental analysis, and single-crystal X-ray analysis. The structure is based on two types of polymeric chains, the anionic one constructed by the coordination interaction between the [b-Mo 8 O 26 ] 4- cluster anions and [Na 2 ] 2+ units, and the cationic one formed through the coordination interaction of Cu(II) atoms and dpdo ligands. In addition, there are multiform hydrogen bonds and π … π interactions in a three-dimensional supramolecular network Graphical Abstract Synthesis and Crystal Structure of a Copper(II) Inorganic-Organic Hybrid Polymer Based on [ß-Mo 8 O 26 ] 4- and 4,4'-Bipyridine-N,N'- dioxide

Treatment of Ru(acac) 3 with 2-cyano-pyridine and 3,5-dimethyl-pyridine in the presence of zinc dust as reducing agent in refluxing THF afforded the ruthenium(II) complexes cis-[Ru II (acac) 2 (2- CN-py) 2 ] (1) and cis-[Ru II (acac) 2 (3,5-Me 2 -py) 2 ] (2), respectively. Interaction of Ru(acac) 3 with 3- Me-pyridine and 3,5-Me 2 -pyridine in the presence of Br 2 in refluxing THF gave the ruthenium(III) complexes [Ru III (acac)Br 2 (3-Me-py) 2 ] (3) and [RuIII(acac)Br 2 (3,5-Me 2 -py) 2 ] (4), respectively. The four complexes have been spectroscopically and electrochemically characterized, and their crystal and molecular structures have been established by X-ray crystallography Graphical Abstract Syntheses, Crystal Structures and Electrochemical Properties of Acetylacetonato-Ruthenium Complexes Containing Substituted Pyridine Ligands

Co(II) nitrate reacts with potassium 5-[(2-methyl-1H-imidazol-1-yl)methyl]isophthalate (K Graphical Abstract Co(II) and Cd(II) Complexes Based on 5-[(2-Methyl-1H-imidazol-1- yl)methyl]isophthalate: Syntheses, Characterization and Properties

The hydrothermal reaction of Zn(II) nitrate with 5-(pyridin-2-ylmethylamino)isophthalic acid (H2L) yields the complex [Zn(L)(H 2 O)] 2H 2 O (1). When 2,2'-bipyridine (bpy) as auxiliary ligand and Cd(II) nitrate were used in the alkaline reaction system, [Cd(L)(H 2 O)(bpy)] 3H 2 O (2) was obtained. Complexes 1 and 2 have been characterized by single-crystal and powder X-ray diffraction, IR, elemental and thermogravimetric analyses. Complex 1 shows a 2D fes network structure with uninodal 3-connected (4.8 2 ) topology, which is further linked by hydrogen bonding to give rise to a 3D supramolecular framework; complex 2 displays a chain structure. Interestingly, tetranuclear water clusters were generated in 1, which are interlinked to fabricate a water chain structure. The fluorescence properties of 1 and 2 were investigated Graphical Abstract Syntheses, Structural Characterization and Fluorescence of Zn(II) and Cd(II) Polymers from 5-(Pyridin-2-ylmethylamino)isophthalic acid

A new Mn(II) metal-organic framework, [Mn(DFDC)(phen)]n (1) (where H 2 DFDC=9,9- diethylfluorene-2,7-dicarboxylic acid, phen=1,10-phenanthroline), was solvothermally synthesized and characterized by single-crystal and powder X-ray diffraction (PXRD), elemental and thermal analysis, IR, UV=Vis spectroscopy, fluorescence and magnetic measurements. Single-crystal X-ray analysis reveals that 1 exhibits a three-dimensional coordination polymer structure. The compound crystallizes in the orthorhombic space group Pnna with a=9.1215(9), b=26.436(3), c=10.2428(10) Å, V =2469.9(4) Å 3 , Z =4, final wR2=0.1323 for 2825 reflections. The Mn(II) ion is coordinated by four oxygen atoms from four different H 2 DFDC ligands and two nitrogen atoms from one phen ligand in an octahedral coordination geometry. The compound shows ferromagnetic coupling behavior and has high thermal stability up to 420 °C Graphical Abstract Synthesis, Crystal Structure and Magnetic Properties of a Mn(II) Fluorenedicarboxylate Complex

The TiCl 4 -mediated cyclization of 1,3-bis(silyloxy)-1,3-butadienes with 2-acetyl-1-silyloxybut-1- en-3-one and 3-acetyl-4-silyloxypent-3-en-2-one, readily available from 3-(formyl)acetylacetone and 3-(acetyl)acetylacetone (triacetylmethane), afforded a variety of functionalized acetophenones Graphical Abstract Synthesis of Functionalized Acetophenones by Formal [3+3] Cyclocondensations of 1,3-Bis(silyloxy)-1,3-butadienes with 3-Alkoxyand 3-Silyloxy-2-acetyl-2-en-1-ones

Reactions of 4-hydroxycoumarin (1a) and 4-chlorocoumarin-3-carbaldehyde (1b) with amino alcohols or alkylene diamines led to the formation of the corresponding N-substituted 4-aminocoumarins 3, 5 and 6. However, 4-hydroxycoumarin-3-carbaldehyde (8) reacted with 2-aminoethanol and ethylenediamine to give N-substituted 3-(aminomethylene)-chromane-2,4-diones 9a, b. The structure and the E-configuration of compound 6 were proven by X-ray crystal structure analysis. Products 9a, b displayed signals of both E- and Z-isomers in their NMR spectra. All novel products have been characterized by means of spectral (IR, NMR, MS) data and elemental analyses Graphical Abstract Synthesis of 4-Aminocoumarin Derivatives with N-Substitutents Containing Hydroxy or Amino Groups

Two new limonoids, 1-O-deacetyl-2a-methoxykhayanolide (1) and kigelianolide (2), together with deacetylkhayanolide E (3), 1-O-deacetyl-2α-hydroxykhayanolide E (4) and khayanolide B (5) were isolated from the ethyl acetate-soluble fraction of the methanolic extract of Kigelia africana. The structures of these limonoids (1-5) were elucidated by the combination of 1D (1H and 13 C NMR) and 2D (HMQC, HMBC and COSY) NMR spectroscopy and mass spectrometry (EIMS, HREIMS), and in comparison with literature data of related compounds. The structure of compound 1 was further confirmed by X-ray crystallography, and the absolute stereochemistry of compounds 1 and 2 was determined by electronic circular dichroism (ECD) spectroscopy. Limonoids 1-5 showed weak inhibitory activities against the enzymes acetylcholinesterase (AChE), butyrycholinesterase (BChE) and lipoxygenase (LOX) in a concentration-dependent manner with IC 50 values in the ranges 137.5 - 225.2 μM for AChE, 185.4 - 241.5 μM for BChE and 281.2 - 189.6 μM for LOX Graphical Abstract Isolation and Characterization of Limonoids from Kigelia africana

A model N-ethyl-1,10-dioxo-3-phenylpyrano[3,2- f ]quinoline-9-carboxylic acid (8) and the isomeric (2-substituted) pyrano[2,3- f ]quinoline-9-carboxylic acids (6 and 7) were prepared from the corresponding 6/7-aminochromen-4-ones via the Gould-Jacobs reaction. The new tricyclic heterocycles 6-8 exhibit moderate antibacterial activity (MIC=16 - 64 μgmL -1 ) against E. coli and S. aureus Graphical Abstract Heterocycles [f]-Fused onto Quinolones. Synthesis of Novel Dioxo-Nethylpyrano[ 2,3-f ]- and [3,2-f ]quinoline-10-carboxylic Acids