Selective Catalytic Isomerization of ß-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate.

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of ß-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO3 ]4 under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.

Direct cyclohexanone oxime synthesis via oxidation-oximization of cyclohexane with ammonium acetate.

An unexpected cascade reaction for oxidation-oximization of cyclohexane with ammonium acetate was developed for the first time to access cyclohexanone oxime with 50.7% selectivity (13.6% conversion). Tetrahedral Ti sites in Ni-containing hollow titanium silicalite can serve as bifunctional catalytic centers in the reaction. This methodology not only provides a direct approach to prepare cyclohexanone oxime, but also simplifies process chemistry. Various available nitrogen sources, such as ammonium salt and even ammonia can be used as starting materials.

Chirality-Helicity Equivalence in the S and R Stereoisomers: A Theoretical Insight.

We located the unknown chirality-helicity equivalence in molecules with a chiral center, and as a consequence, the degeneracy of the S and R stereoisomers of lactic acid was lifted. An agreement was found with the naming schemes of S and R stereoisomers from optical experiments. This was made possible by the construction of the stress tensor trajectories in a non-Cartesian space defined by the variation of the position of the torsional bond critical point upon a structural change, along the torsion angle, θ, involving a chiral carbon atom. This was undertaken by applying a torsion θ, -180.0° ≤ θ ≤ +180.0° corresponding to clockwise and counterclockwise directions. We explain why scalar measures can at best only partially lift the degeneracy of the S and R stereoisomers, as opposed to vector-based measures that can fully lift the degeneracy. We explained the consequences for stereochemistry in terms of the ability to determine the chirality of industrially relevant reaction products.

Imidazolyl activated carbon refluxed with ethanediamine as reusable heterogeneous catalysts for Michael addition.

Imidazolyl activated carbon, denoted as AC-N, was prepared via oxidation of AC with HNO3 (AC-O) and then refluxed with ethanediamine under mild conditions. The results showed that the N content of AC-N was 10.3%, and the surface alkali group density of AC-N was 0.96 mmol g-1 from 0.78 mmol g-1 carboxy group of AC-O by Boehm titration. It was revealed that the basic functional groups on the AC-N surface included imidazole and amine groups, from XPS and FT-IR. Evaluated with Michael addition of furfural, the catalytic performance of AC-N showed higher conversion and selectivity than that of commonly used base catalyst such as 2-methylimidazole and KOH. Very remarkably, AC-N showed extraordinary recyclability, in that there was no decline of conversion and selectivity after being recycled 5 times.

π-Extended "Earring" Porphyrins with Multiple Cavities and Near-Infrared Absorption.

ß,ß-tripyrrin-bridged earring porphyrins were synthesized through Suzuki-Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x-ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near-infrared (NIR) absorptions and metal insertion leads to red-shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties.

Azobenzene-Bridged Porphyrin Nanorings: Syntheses, Structures, and Photophysical Properties.

Azobenzene-bridged ß-to-ß and meso-to-meso porphyrin nanorings were successfully synthesized by a palladium-catalyzed Suzuki-Miyaura coupling reaction in a logical synthesis. The dimeric structure was confirmed by XRD analysis. The azo linkages in di- and tetramers are in the all-trans conformation, whereas in the trimers one azo linkage can be interconverted between cis and trans under external stimulation. When trimeric isomers are heated to 333 K or higher, the azo linkages will be in the all-trans configurations: the pure all-trans trimer can be kept in the dark for several months. Fluorescence anisotropy and pump-power-dependent decay results revealed excitation energy transfer for azobenzene-bridged zinc-porphyrin nanorings. The distances between porphyrin units of these azobenzene-bridged porphyrin arrays are almost the same, but the exciton energy hopping (EEH) times for each wheel are markedly different. The dimer and meso-to-meso tetramer possess relatively short excitation energy transfer (EET) times (1.28 and 2.48 ps, respectively) due to their good planarity and rigidity. In contrast, the EET time for the trimeric zinc(II)-porphyrin array (6.9 ps) is relatively long due to its nonradiative decay pathway (i.e., cis/trans isomerization of azobenzene). Both di- and tetramers exhibit relatively high fluorescence quantum yields, whereas the trimers show weak emission because of structural differences.

Hybrid QTAIM and electrostatic potential-based quantum topology phase diagrams for water clusters.

The topological diversity of sets of isomers of water clusters (W = H2O)n, 7 ≤ n ≤ 10, is analyzed employing the scalar fields of total electronic charge density ρ(r) and the molecular electrostatic potential (MESP). The features uncovered by the MESP are shown to be complementary to those revealed by the theory of atoms in molecules (QTAIM) analysis. The MESP is known to exhibit the electron localizations such as lone pairs that are central to water cluster behavior. Therefore, a 'hybrid' QTAIM and MESP quantum topology phase diagram (QTPD) for Wn, 7 ≤ n ≤ 10, is introduced in addition to the QTPD. The 'spanning' QTPD with upper and lower bounds is constructed from the solutions of the Poincaré-Hopf relation involving the non-degenerate critical points. The changing subtle balance between the planar and three dimensional character of the growing water clusters Wn, 4 ≤ n ≤ 10, is revealed. Characterization of the structure of the QTPDs, possible with new tools, demonstrated the migration of the position of the global minimum on the spanning QTPD from the lower bound to upper bound as the Wn, 4 ≤ n ≤ 10, cluster grows in size. Differences in the structure of the QTPD are found between the clusters containing even versus odd monomers for Wn, n = 7-10. The energetic stability of the clusters which possess even number of monomers viz. n = 8, 10 is higher than that of the n = 7, 9 clusters due to relatively higher numbers of hydrogen-bond BCPs in the n = 8, 10 clusters, in agreement with energetic results reported in the literature. A 'hybrid' QTPD is created from a new chemical relation bHB + l ≥ 2n for Wn that relates the number of hydrogen-bond bond critical points (bHB) with the number of oxygen lone pairs exclusively specified by the negative valued MESP (3,+3) critical points (l). The topologies of the subset bHB + l = 2n for Wn, point the way to the discovery of unknown 'missing' lower energy isomers. A discussion of the relative merits and range of applicability of the QTAIM and hybrid-QTPD analyses is included and concludes that the hybrid-QTPD analysis for Wn, is more useful for the association with the energy minima on the potential energy surface.

Structures, energies and bonding in neutral and charged Li microclusters.

Structural and chemical properties of charged and neutral Lithium microclusters are investigated for [Formula: see text]. A total of 18 quantum conformational spaces are randomly walked to produce candidate structures for local minima. Very rich potential energy surfaces are produced, with the largest structural complexity predicted for anionic clusters. Analysis of the electron charge distributions using the quantum theory of atoms in molecules (QTAIM) predicts major stabilizing roles of Non-nuclear attractors (NNAs) via NNA···Li interactions with virtually no direct Li···Li interactions, except in the least stable configurations. A transition in behavior for clusters containing more than seven nuclei is observed by using the recently introduced quantum topology to determine in a quantum mechanically consistent fashion the number of spatial dimensions each cluster has. We experiment with a novel scheme for extracting persistent structural motifs with increase in cluster size. The new structural motifs correlate well with the energetic stability, particularly in highlighting the least stable structures. Quantifying the degree of covalent character in Lithium bonding independently agrees with the observation in the transition in cluster behavior for lithium clusters containing more than seven nuclei. Good correlation with available experimental data is obtained for all properties reported in this work.