Intercalation of heterocyclic compounds in α-zirconium phosphate: Imidazole,benzimidazole, histamine and histidine

The intercalation of imidazole and some organic species containing the imidazole ring, between the layers of crystalline zirconium phosphate has been investigated. Fourteen new, well-ordered intercalation compounds are obtained with the batch procedure at r.t. and/or 60°C. A mechanism of formation of the various compounds is proposed on the basis of the interaction between the guest molecules (with their dimensions and geometries) and the free PO₃OH groups available between the layers of the host. The new phases have been characterized by TG and X-ray methods.     

Coordinating properties of C2-symmetric chiral bis(oxazolinylpyridinyl)dioxolane ligands

Metal complexes of general formula M(L)X₂ and M(L)X₃ [L = (4S,5S)-2,2-dimethyl-4,5-bis{6-[(4,5-dihydro-4-(S)-(1-methylethyl)oxazol-2-yl)pyridin-2-yl]}-1,3-dioxolane] were obtained by reacting, respectively, Co^II, Cu^II, Ni^II, and Zn^II nitrate salts and the Rh^III chloride salt, with a chiral C₂-symmetric bis(oxazolinylpyridinyl)dioxolane (L) ligand, in MeOH/CHCl₃ solution. A single crystal X-ray analysis was carried out on [Ni(L)(OH₂)₂](NO₃)₂ · 2H₂O and the molecular structure of L was also determined. In the free ligand the two symmetric arms are essentially planar and oriented nearly perpendicular to the dioxolane average plane. In the Ni complex one seven-membered and two five-membered chelation rings are formed. The metal atom also lies on the C₂ axis, and two symmetry-related water molecules complete the octahedral coordination environment. Both compounds crystallize in chiral space groups; the ligand crystallizes in orthorhombic system, space group C 2 2 2₁, Z = 4; the nickel complex crystallizes in tetragonal system, space group P 4₃ 2₁ 2, Z = 4.     

Discrete negative refraction in photonic crystal waveguide arrays

We report a systematic analysis of anomalous refractive effects at interfaces between two photonic crystal waveguide arrays. Discrete negative refraction can be easily predicted from the sign of the coupling coefficient between adjacent waveguides, regardless of handedness of propagation.     

Heterocyclic compounds studies. Dynamic 13C NMR investigation and crystal structure of 3-hydroxy-1,5-benzoxathiepine

1-5-benzoxathiepine compounds are a novel class of heterocyclic rings that present interesting properties as central nervous system depressants. With the aim to contribute to the elucidation of the structure-activity relationship of this class of compounds we report a structural study of the 3-hydroxy-1,5-benzoxathiepine both in solution and in the solid state. Studies by dynamic ¹³C-nmr in solution show that three conformations are possible for the oxathiepin ring. A unique chair conformation characterizes the atoms in the oxathiepine ring of the crystallized molecule. The crystal structure was solved by direct methods. Values of bond distances and angles are within the expected range.     

Diffraction engineering in arrays of photonic crystal waveguides

Light propagation in uniform arrays of photonic crystal waveguides is studied. We demonstrate that, in stark contrast to the case of conventional waveguide arrays, diffraction can be tailored both in magnitude and sign by varying only the spacing between adjacent waveguides. Diffraction management in ultracompact arrays of straight photonic crystal waveguides is demonstrated by solving Maxwell's equations through the time-domain finite-element method.     

Influence of organic modifier and temperature on the enantiomeric separation of γ-lactams by HPLC

Summary A high-performance liquid chromatographic method is reported for the resolution of the enantiomers of a series of fused -lactams (2,7-diaza-3-oxo[3.3.0]octan-6-ones) with probable anti-HIV and anticancer activity. Resolution was achieved on a Chiralcel^® OD column, cellulose tris-(3,5-dimethylphenyl carbamate) adsorbed on macroporous silica gel; mixtures ofn-hexane and isopropyl alcohol in different proportions were used as the mobile phase. The analysis was studied at different temperatures.     

ac conductivity of anhydrous pellicular zirconium phosphate in hydrogen form

Aqueous suspensions of delaminated zirconium phosphate have been recently obtained in our laboratory by a suitable intercalation-deintercalation of alkylamines. By filtering these suspensions thin and flexible sheets or pellicles of lamellar α-zirconium phosphate, with the most part of the layers oriented parallel to the pellicle surface, can be easily prepared. ac conductivity measurements have been carried out, in the temperature range 150–300°C, on pellets made of α-Zr(HPO₄)₂ pressed pellicles, oriented both parallel and perpendicular to the electric field. Independently of the pellet orientation, a slope variation was observed in the Arrhenius plot at about 220°C. As already found for the α-Zr(HPO₄)₂ powder, this is associated with a phase transition at this temperature, which causes a discontinuous change of the interlayer distance from 7.4 Å to 6.8 Å. The conductivity of samples oriented parallel to the electric field ($\text{～10}{}^{\mathrm{?4}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{at}\text{300°}\text{C}$) is about two orders higher than the conductivity of the anhydrous microcrystalline powder, which, in turn, is higher than that of perpendicularly oriented samples ($\text{～3 × 10}{}^{\mathrm{?7}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{at}\text{300°}\text{C}$).     

The influence of ligand field effects on the magnetic exchange of high-spin Co(II)-semiquinonate complexes

[Co(Me(4)cyclam)(tropolonate)](PF(6)) was synthesised and structurally characterised. Its electronic and W-band EPR spectra have been analysed by means of the angular overlap calculation of the Spin Hamiltonian parameters that provided also a satisfactory reproduction of the temperature dependence of the magnetic susceptibility. The present results can be interpreted assuming a pseudo-octahedral character for the Co(II) center. This prompted us to reconsider the model formerly used for the analysis of the magnetic coupling between hs-Co(II) and the paramagnetic o-semiquinonate ligand in the corresponding derivatives [Co(Me(4)cyclam)(PhenSQ)](PF(6)) and [Co(Me(4)cyclam)(DTBSQ)](PF(6)). These results indicate that the effect of the magnetic coupling is active only below 50 K and that a more refined model of exchange coupling between Co(II) and semiquinonato ligands is needed to quantitatively analyze the magnetic behaviour of this class of systems.     

Light propagation in nonuniform plasmonic subwavelength waveguide arrays

We study light propagation in nanoscale periodic structures composed of dielectric and metal in the visible range. We demonstrate that diffraction curves of nonuniform waveguide arrays can be tailored by varying the geometric and dielectric features of the waveguides. The results obtained from a proper formulation of coupled mode theory for nonuniform arrays are validated through numerical solution of Maxwell equations in frequency domain.