Transition metal complexes with 2-methyl-, 3-methyl-, and 4-methyl-piperidine dithiocarbamate as ligands

Summary A new series of manganese(III), cobalt(II), nickel(II), zinc(II), cadmium(II) and mercury(II) complexes with monomethylsubstituted dithiocarbamates as ligands has been synthesized and studied. Their structures are discussed in relation to their spectroscopic, magnetic and thermal properties. The dithio-ligands exhibit bidentate behaviour acting as S,Sdonors in all the complexes. In the far i.r. region particular attention is paid to a comparison of the spectra of the octahedral complexes with those of the other metal derivatives (12 metal to ligand molar ratio). The e.s.r. spectra are indicative of aD _2h symmetry in the cobalt(II) complexes.     

Improved Schemes for Visual Cryptography

A (k,n)-threshold visual cryptography scheme ((k,n)-threshold VCS, for short) is a method to encode a secret image SI into n shadow images called shares such that any k or more shares enable the visual recovery of the secret image, but by inspecting less than k shares one cannot gain any information on the secret image. The visual recovery consists of xeroxing the shares onto transparencies, and then stacking them. Any k shares will reveal the secret image without any cryptographic computation.In this paper we analyze visual cryptography schemes in which the reconstruction of black pixels is perfect, that is, all the subpixels associated to a black pixel are black. For any value of k and n, where 2 k n, we give a construction for (k,n)-threshold VCS which improves on the best previously known constructions with respect to the pixel expansion (i.e., the number of subpixels each pixel of the original image is encoded into). We also provide a construction for coloured (2,n)-threshold VCS and for coloured (n,n)-threshold VCS. Both constructions improve on the best previously known constructions with respect to the pixel expansion.     

Photoluminescence Efficiency of Substituted Quaterthiophene Crystals

The photoluminescence (PL) efficiency of substituted alpha-conjugated quaterthiophene crystals shows marked differences depending on crystal packing and molecular geometry. This effect is studied by evaluating the role of the intermolecular interactions and the effects of the single molecule conformation on the intersystem crossing (ISC) rate. The comparison of these calculations with absolute quantum efficiency measurements and with the experimental temperature dependence of the PL decay time, indicates that the differences in PL efficiency are not inherent to crystal packing effects but they are determined by the ISC rate.     

Synthesis of optically active constrained 2-substituted norstatines: a straightforward application of Seebach's "SRS" synthetic principle

A straightforward two-step methodology of synthesis of optically active (2R)-substituted norstatines via addition of N-tert-butoxycarbonyl-substituted aldimines to (2S)-chiral enolates of 1,3-dioxolan-4-ones has been developed. In particular, the use of the natural (2S)-malic acid is examined for the synthesis of potential GABAergic spirocyclic gamma-lactams.     

Synthesis and characterization of β-fused porphyrin-BODIPY dyads

Novel dyads in which a porphyrin ring is directly fused through two β-pyrrolic carbons to a BODIPY^® moiety have been prepared using a stepwise approach starting from the copper(II) complex of pyrrolo[2,3-c]-5,10,15,20-tetraphenylporphyrin. Formylation and reaction with 3,5-dimethylpyrrole afforded 8; subsequent BF₂ complexation gave the TPP-BODIPY^® dyad in reasonable yields. Demetalation in TFA/H₂SO₄ led to the corresponding free base 12, opening the way to the subsequent preparation of the Zn complex 13. Both 12 and 13 exhibited complex optical spectra with an intensely red-shifted Q-band. Luminescence spectra displayed a very intense band around 700 nm making these species suitable as near-IR dyes and sensors in biological media. Optical analyses of 12, using the INDO/SCI technique, were performed to obtain information to establish the origin of the novel optical properties. These studies showed that the optical properties of 12 cannot be attributed to deformation of the molecular skeleton, but derive from the increased extension of the conjugation between the TPP and BODIPY^® π-systems.