Electron density distribution in potassium bis -(carbonato)cuprate(II)

The electron density distribution in potassiumbis-(carbonato)cuprate(II) has been analyzed using x-ray diffraction data from an earlier structure determination. While the copper-ligand geometry is close to square planar the deformation density near the metal is strongly asymmetric. There are local maxima near the copper atom along the line of the Cu-K vectors. These resemble features found in corresponding regions in normal length metal-metal bonds. The observation is consistent with the long range nature of the Coulomb potential associated with the potassium ion.     

A hexa-peri-hexabenzocoronene cyclophane: an addition to the toolbox for molecular electronics

Cyclophanes with the largest-to-date polycyclic aromatic hydrocarbon (hexa-peri-hexabenzocoronene, HBC) to be entrained in such a structural motif are reported. The two disks are covalently captured by intermolecular ring-closing olefin metathesis of dienes in good yield. DSC, optical microscopy, and WAXD show the new cyclophanes to self-assemble to thermotropic columnar liquid crystal mesophases similar to monomeric analogues. Solution spectroscopic studies reveal that the two disks within a single unit lie face-to-face, with a small average lateral offset. Self-assembly into two-dimensional crystals at a solid-liquid interface was visualized by STM, and the electrical properties of single molecules were assessed by scanning tunneling spectroscopy revealing a diode-like behavior which is similar to that previously reported for single HBC disks, laying the groundwork for future electrical interrogations of dynamic molecular complexes.     

The di-π-methane rearrangement : The effect of 1,4-diene structure and conformation on the reaction efficiency and stereochemistry

The photochemistry of the stereoisomeric 1,3-dimethyl-3(2-phenylethenyl)cyclohexenes has been explored Direct irradiation of the cis- and trans-β-styrylcyclohexenes leads to di-π-methane rearrangement, producing the endo- and exo-3,7-dimethyl-8-phenybicyclo[5.1.0]oct-2-enes, and cis -trans isomerization, interconverting the 1,4-diene containing substrates. Triplet sensitized photolysis of both substituted cyclohexenes leads exclusively to cis-trans isomerization. Results from low conversion direct irradiations of the cis- and trans-β-styrylcyclohexenes indicate that the singlet rearrangements are stereospecific, and lead to formation of the 8-exo and 8-endo-phenylbicyclic octenes, respectively. The relationship between di-π-methane structure and triplet reaction efficiency, and the effect of conformation on the rearrangement stereochemistry are discussed.     

Calculating the knowledge-based similarity of functional groups using crystallographic data

A knowledge-based method for calculating the similarity of functional groups is described and validated. The method is based on experimental information derived from small molecule crystal structures. These data are used in the form of scatterplots that show the likelihood of a non-bonded interaction being formed between functional group A (the `central group') and functional group B (the `contact group' or `probe'). The scatterplots are converted into three-dimensional maps that show the propensity of the probe at different positions around the central group. Here we describe how to calculate the similarity of a pair of central groups based on these maps. The similarity method is validated using bioisosteric functional group pairs identified in the Bioster database and Relibase. The Bioster database is a critical compilation of thousands of bioisosteric molecule pairs, including drugs, enzyme inhibitors and agrochemicals. Relibase is an object-oriented database containing structural data about protein-ligand interactions. The distributions of the similarities of the bioisosteric functional group pairs are compared with similarities for all the possible pairs in IsoStar, and are found to be significantly different. Enrichment factors are also calculated showing the similarity method is statistically significantly better than random in predicting bioisosteric functional group pairs.     

Tuning the optical properties of fluorinated indolylfulgimides

Photochromic fluorinated indolylfulgides have been identified as potential candidates for a wide range of applications including optical switches, photoregulators of biological processes, and optical memory media. In humid environments or biological systems, hydrolytic stability is essential. In an effort to improve hydrolytic stability, a series of indolylfulgimides has been synthesized from a parent trifluoromethyl-substituted indolylfulgide. The nitrogen of the succinimide moiety is linked to either a dimethyl amino or one of seven substituted phenyl groups. The phenyl groups feature substituents with increasing electron-withdrawing ability. The spectral characteristics of each compound have been examined, revealing that the wavelength absorption maxima of each form increases with increasing electron-withdrawing ability of the substituted N-phenyl ring. The quantum yields of the photoreactions have been determined with the N-(phenyl)fulgimide showing a ring closure value of nearly 0.30 in toluene. In addition, the hydrolytic, thermal, and photochemical stabilities of each compound have been measured. The fulgimides exhibit at least a 200-fold enhancement of hydrolytic stability for the Z-form and over a 1000-fold enhancement for the C-form in comparison to the same form of the parent fulgide. The N-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)fulgimide can undergo up to 3000 photochemical cycles (coloration followed by bleaching) before losing 20% of its initial absorbance at photostationary state.     

Partial order complementation graphs

Two partial ordersP andQ on a setX arecomplementary (written asPQ) if they share no ordered pairs (except for loops) but the transitive closure of the union is all possible ordered pairs. For each positive integern we form a graph Pos _n consisting of all nonempty partial orders on {1, ,n} with edges denoting complementation. We investigate here properties of the graphs Pos _n . In particular, we show: