Structural and spectroscopic studies of nickel(II) complexes with a library of Bis(oxime)amine-containing ligands

A library of tripodal amine ligands with two oxime donor arms and a variable coordinating or noncoordinating third arm has been synthesized, including two chiral ligands based on l-phenylalanine. Their Ni(II) complexes have been synthesized and characterized by X-ray crystallography, UV-vis absorption, circular dichroism, and FTIR spectroscopy, mass spectrometry, and room-temperature magnetic susceptibility. At least one crystal structure is reported for all but one Ni/ligand combination. All show a six-coordinate pseudo-octahedral coordination geometry around the nickel center, with the bis(oxime)amine unit coordinating in a facial mode. Three distinct structure types are observed: (1) for tetradentate ligands, six-coordinate monomers are formed, with anions and/or solvent filling out the coordination sphere; (2) for tridentate ligands, six-coordinate monomers are formed with Ni(II)(NO(3))(2), with one monodentate and one bidentate nitrate filling the remaining coordination positions; (3) for tridentate ligands, six-coordinate, bis(mu-Cl) dimers are formed with Ni(II)Cl(2), with one terminal and two bridging chlorides filling the coordination sphere. The UV-vis absorption spectra of the complexes show that the value of 10 Dq varies according to the nature of the third arm of the ligand. The trend based on the third arm follows the order alkyl/aryl < amide < carboxylate < alcohol < pyridyl < oxime.     

Design Rules for Self‐Assembly of 2D Nanocrystal/Metal–Organic Framework Superstructures

We demonstrate the guiding principles behind simple two dimensional self‐assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe₃O₄) NCs into a uniform two‐dimensional bi‐layered superstructure. This self‐assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe₃O₄ NCs and Zr₆O₄(OH)₄(fumarate)₆ MOF NPs. Scanning transmission electron microscopy (TEM)/energy‐dispersive X‐ray spectroscopy and TEM tomography confirm the hierarchical co‐assembly of Fe₃O₄ NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First‐principles calculations and event‐driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self‐assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self‐assembly process, which could be a guide for designing functional materials with desired structure.     

Proposal for underwater structural analysis using the techniques of ESPI and digital holography

The purpose of this article is to study the application of the holographic interferometry techniques in the structural analysis of submarine environment. These techniques are widely used today, with applications in many areas. Nevertheless, its application in submarine environments presents some challenges. The application of two techniques, electronic speckle pattern interferometry (ESPI) and digital holography, comparison of advantages and disadvantages of each of them is presented. A brief study is done on the influence of water properties and the optical effects due to suspended particles as well as possible solutions to minimize these problems.     

First stereocontrolled acetylation of a hydroxypropargylpiperidone by lipase CALB

Hydroxypropargylpiperidones rac-1–3 were efficiently obtained by a one-pot three-component coupling reaction; enantioenriched propargylpiperidones were then obtained by a kinetic resolution process using the lipase from Candida antarctica. Lipase CALB has been shown to efficiently catalyse the stereocontrolled acetylation of hydroxypropargylpiperidones rac-3 by promoting stereodiscrimination at the carbinolic centre. The enzymatic catalytic processes allow the separation of the (S,R)- and (S,S)-3 diastereoisomers into the corresponding acetates produced as a (R,S)- and (R,R)-6 diastereoisomeric pair. The CALB was able to discriminate the stereogenic centre of the secondary (R)-enantiomer of rac-3 according to the Kaslauzkas rule. The remote stereogenic centre was not discriminated by the lipase. The functionalised enantioenriched diastereoisomers obtained are important building blocks in organic synthesis.     

Analysis of why boron avoids sp2 hybridization and classical structures in the BnHn+2 series

We performed global minimum searches for the B(n) H(n+2) (n=2-5) series and found that classical structures composed of 2c-2e B-H and B-B bonds become progressively less stable along the series. Relative energies increase from 2.9?kcal?mol(-1) in B(2) H(4) to 62.3?kcal?mol(-1) in B(5) H(7). We believe this occurs because boron atoms in the studied molecules are trying to avoid sp(2) hybridization and trigonal structure at the boron atoms, as in that case one 2p-AO is empty, which is highly unfavorable. This affinity of boron to have some electron density on all 2p-AOs and avoiding having one 2p-AO empty is a main reason why classical structures are not the most stable configurations and why multicenter bonding is so important for the studied boron-hydride clusters as well as for pure boron clusters and boron compounds in general.     

SU(N) group-theory constraints on color-ordered five-point amplitudes at all loop orders

Color-ordered amplitudes for the scattering of n particles in the adjoint representation of SU(N) gauge theory satisfy constraints arising solely from group theory. We derive these constraints for n=5 at all loop orders using an iterative approach. These constraints generalize well-known tree-level and one-loop group theory relations.     

γ-Cyanooxazolines: an interesting synthon from oxazoline cyanocuprate addition to conjugated cyanoalkenes

The oxazoline cyanocuprates addition to conjugated cyanoalkenes, was shown to be an efficient method for the synthesis of a variety of γ-cyanooxazolines, interesting intermediates with different, but convertible, functions in a symmetrical position.     

Modelling relaxation processes for fluids in porous materials using dynamic mean field theory: application to pore networks

We present an application of a recently developed dynamic mean field theory to the study of relaxation dynamics in adsorption and desorption from pore networks. The theory predicts the evolution of density distribution in the system, based on an underlying free energy functional from static mean field theory and the system evolves to equilibrium or metastable equilibrium states consistent with the static theory. The theory makes it possible to follow the evolution of the density distribution with time in response to a change in the bulk pressure or chemical potential. We compare uptake dynamics for a 2D slit pore network with that in a single slit pore. We see more rapid uptake dynamics in the pore network in some cases, due to the greater access of the pore space to the bulk. We also observe that the formation of liquid bridges can slow down the mass transfer in the pore network in certain situations.