Tetranuclear manganese(II) complexes of sulfonylcalix[4]arene macrocycles: synthesis, structure, spectroscopic and magnetic properties

Two tetranuclear manganese(II) complexes {K(+)[Mn(4)(ThiaSO(2))(2)(OH)](-)} (1) and {K(+)[Mn(4)(ThiaSO(2))(2)(F)](-)} (2) have been synthesized under solvothermal conditions in methanol with p-tert-butylsulfonylcalix[4]arene (ThiaSO(2)). For both complexes, the structure has been established from single-crystal X-ray diffraction. The two complexes are best described as manganese squares sandwiched between two thiacalixarene macrocycles. In both complexes, in the center of the square formed by the four manganese(II) atoms, the unexpected presence of μ(4)-OH(-) or μ(4)-F(-) gives a negative charge to the cluster. The two tetranuclear complexes exhibit strong orange luminescence behavior resulting from the symbiosis between the ThiaSO(2) and the Mn(2+). Despite similar chemical formulation, (1) and (2) present difference in emission intensity and lifetime τ.     

Synthesis, crystal structure, and spectroscopic study of K0.92(2) Zn0.08(2) H1.92(2) (PO4) (Zn-KDP)

The structure of K0.92₍₂₎ Zn_0.08(2) H_1.92(2) (PO₄) was determined using single-crystal X-ray diffraction. The crystal structure of the Zn-KDP belonged to the tetragonal space group $ \mathrm{I}\overline{4}2\mathrm{d} $ , with cell parameters of a?=?b?=?7.4487(5)?Å and c?=?6.9703(5)?Å, 386.73(5) Å3, Z?=?4, and R?=?0.023. Zn²⁺ ions were used as substitutes for K⁺ ions with hydrogen vacancy. The Zn-KDP single crystals were submitted to further Raman, infrared, and ¹H NMR studies to investigate chemical group functionalisation, possible bonding between the organic and inorganic materials, and partial substitution of K⁺ by Zn²⁺. The latter partial substitution was confirmed by the deviation of IR frequencies for O–H stretching, the variation of IR and Raman frequencies for stretching and bending vibrations ν(PO₄) of H₂PO₄, and the appearance of additional Raman (147, 386 and 481 cm^?1) vibrational bands. Electrical conductivity measurements were performed on polycrystalline pellets of Zn-KDP and pure KDP at room temperatures (RT) of up to 473K. In both cases, a conductivity jump close to 453K was observed, and a stronger increase of conductivity was measured.     

Structural characterization,thermal, ac conductivity and dielectric properties of (C7H12N2)2[SnCl6]Cl2·1.5H2O

(C₇H₁₂N₂)₂[SnCl₆]Cl₂·1.5H₂O is crystallized at room temperature in the monoclinic system (space group P2₁/n). The isolated molecules form organic and inorganic layers parallel to the (a, b) plane and alternate along the c-axis. The inorganic layer is built up by isolated SnCl₆ octahedrons. Besides, the organic layer is formed by 2,4-diammonium toluene cations, between which the spaces are filled with free Cl^? ions and water molecules. The crystal packing is governed by means of the ionic N—H···Cl and Ow—H···Cl hydrogen bonds, forming a three-dimensional network. The thermal study of this compound is reported, revealing two phase transitions around 360(±3) and 412(±3) K. The electrical and dielectric measurements were reported, confirming the transition temperatures detected in the differential scanning calorimetry (DSC). The frequency dependence of ac conductivity at different temperatures indicates that the correlated barrier hopping (CBH) model is the probable mechanism for the ac conduction behavior.     

Synthesis and X-ray structure of cationic methallyl palladium complexes supported by unsymmetrical β-diimine ligands

Treatment of the unsymmetrical β-iminoamine ligands [PhCN(Ar)CHCNH(Ar)Me] with the zerovalent complex Pd(dba)₂ in the presence of the methallyloxyphosphonium salt, gives high yields of the cationic β-diimine complexes [PhCN(Ar)CH₂CN(Ar)(Me)Pd(η³-C₄H₇)]⁺[PF₆]⁻ (Ar = 2-Me-C₆H₄ (7); 2-MeO-C₆H₄ (8); 2,6-Me₂-C₆H₃ (9); 2,6-iPr₂-C₆H₃ (10)). All the new complexes have been characterised by NMR and IR spectroscopy. The structure of the cationic methallyl palladium complex (10) has been solved by X-ray crystallography.     

Chemical preparation and crystal structure of 6′-butoxy-2,6-diamino-3,3′azo-dipyridine monohydrate

Chemical preparation, X-ray single crystal, and calorimetric studies of C₁₄H₁₈N₆O·H₂O are described. The compound crystallizes in the triclinic space group, P with unit cell dimensions: a = 6.2640(3), b = 10.9840(4), c = 12.2220(3) Å, = 105.03(2), = 96.96(2), = 101.6(2)°, V = 712.10(5) ų, and Z = 2. The 6-butoxy-2,6-diamino-3,3-azo-dipyridine monohydrate structure is built up from organic layers parallel to the (120) plane linked via O—H···N bond.     

Circularly Polarized Fluorescent Helicene-Boranils: Synthesis,Photophysical and Chiroptical Properties

Mono- and di-boranil-substituted helicenes were prepared by BF₂-borylation of the corresponding anils, readily synthesized by condensation of 2-amino- and 2,15-diamino-helicenes with 4-(diethylamino)salicylaldehyde. After enantiomeric resolution using HPLC, their chiroptical properties including circularly polarized fluorescence in solution and in PMMA films were investigated and rationalized with the help of NMR, X-ray and quantum-chemical calculations.     

Conductivity study by complex impedance spectroscopy of solid solution AgxK1 − xNb4AsO13 (x = 0.2 and 0.62): effect of the substitution of K+ by Ag+ cations on the ionic conduction properties

Journal of Solid State Electrochemistry - Crystals of Ag0.2K0.8Nb4AsO13 (I) and Ag0.62K0.38Nb4AsO13 (II) were synthesized by a solid-state reaction. Both of them crystallize in the orthorhombic...     

Reconstruction of a defect in an open waveguide

The paper is concerned with the reconstruction of a defect in the core of a two-dimensional open waveguide from the scattering data. Since only a finite numbers of modes can propagate without attenuation inside the core, the problem is similar to the one-dimensional inverse medium problem. In particular, the inverse problem suffers from a lack of uniqueness and is known to be severely ill-posed. To overcome these difficulties, we consider multi-frequency scattering data. The uniqueness of solution to the inverse problem is established from the far field scattering information over an interval of low frequencies.