Facile purification of rare cucurbiturils by affinity chromatography

A practical method for the separation and purification of cucurbituril (CB) hexamers was developed on the basis of affinity chromatography using aminopentylaminomethylated polystyrene beads. This recyclable resin, which can be used repeatedly, facilitates the general preparation of cucurbituril derivatives and compensates for the usually moderate yields and mixed products that characterize the acid-catalyzed synthesis of CB derivatives. This technique allows convenient, rapid isolation of rare substituted cucurbiturils, including hexacyclohexanocucurbit[6]uril and dodecamethylcucurbit[6]uril. [reaction: see text]     

Intramolecular [2 + 2] photocycloaddition of alkenes incorporated in a carbohydrate template. Synthesis of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes

Intramolecular [2 + 2] photocycloaddition of alkenes with a furano sugar placed between them have been investigated under both copper(I)-catalyzed and sensitized conditions. The copper(I)-catalyzed photocycloaddition of the dienes 4a, 4b, and 4c led to unexpected formation of the thermodynamically less stable cis-syn-cis 4-5-5 tricyclic adducts 5a, 5b, and 5c, respectively. The sensitized photocycloaddition of the diene 14 also gave the cis-syn-cis adduct 15 showing that the copper(I) catalyst does not have any influence on the stereochemical course through coordination with the anomeric ring oxygen of the furano sugar. The identical stereochemical course observed under both catalyzed and sensitized photoaddition reactions have been attributed to be of steric origin. Bis(dienes) 25a and 25b, which gave an intractable mixture on copper(I)-catalyzed irradiation, underwent smooth photocycloaddition in the presence of benzophenone, and the resulting 1,2-divinyl cyclobutanes underwent spontaneous [3.3]-rearrangement at room temperature to produce bicyclo[6.3.0]undecanes 30a and 30b, respectively. This investigation provides an approach for the construction of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes.     

An Ultra-Microporous Metal–Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO₂. Further ¹²⁹Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.     

Unusual Surface Latent Heat Flux Variations and Their Critical Dynamics Revealed before Strong Earthquakes

We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock.     

Magnetic exchange interactions and magneto-structural correlations in heterobridged μ-phenoxo-μ(1,1)-azide dinickel(II) compounds: a combined experimental and theoretical exploration

This investigation presents the syntheses, crystal structures, magnetic properties, and density functional theoretical modeling of magnetic behavior of two heterobridged μ-phenoxo-μ(1,1)-azido dinickel(II) compounds [Ni(II)(2)(L(1))(2)(μ(1,1)-N(3))(N(3))(H(2)O)]·CH(3)CH(2)OH (1) and [Ni(II)(2)(L(2))(2)(μ(1,1)-N(3))(CH(3)CN)(H(2)O)](ClO(4))·H(2)O·CH(3)CN (2), where HL(1) and HL(2) are the [1+1] condensation products of 3-methoxysalicylaldehyde and 1-(2-aminoethyl)-piperidine (for HL(1))/4-(2-aminoethyl)-morpholine (for HL(2)), along with density functional theoretical magneto-structural correlations of μ-phenoxo-μ(1,1)-azido dinickel(II) systems. Compounds 1 and 2 crystallize in orthorhombic (space group Pbca) and monoclinic (space group P2(1)/c) systems, respectively. The coordination environments of both metal centers are distorted octahedral. The variable-temperature (2-300 K) magnetic susceptibilities at 0.7 T of both compounds have been measured. The interaction between the metal centers is moderately ferromagnetic; J = 16.6 cm(-1), g = 2.2, and D = -7.3 cm(-1) for 1 and J = 16.92 cm(-1), g = 2.2, and D(Ni1) = D(Ni2) = -6.41 cm(-1) for 2. Broken symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and provide a good numerical estimate of J values (15.8 cm(-1) for 1 and 15.35 cm(-1) for 2) compared to experiments. The role of Ni-N bond length asymmetry on the magnetic coupling has been noted by comparing the structures and J values of complexes 1 and 2 together with previously published dimers 3 (Eur. J. Inorg. Chem. 2009, 4982), 4 (Inorg. Chem. 2004, 43, 2427), and 5 (Dalton Trans. 2008, 6539). Our extensive DFT calculations reveal an important clue to the mechanism of coupling where the orientation of the magnetic orbitals seems to differ with asymmetry in the Ni-N bond lengths. This difference in orientation leads to a large change in the overlap integral between the magnetic orbitals and thus the magnetic coupling. DFT calculations have also been extended to develop several magneto-structural correlations in this type of complexes and the correlation aim to focus on the asymmetry of the Ni-N bond lengths reveal that the asymmetry plays a proactive role in governing the magnitude of the coupling. From a completely symmetric Ni-N bond length, two behaviors have been noted: with a decrease in bond length there is an increase in the ferromagnetic coupling, while an increase in the bond lengths leads to a decrease in ferromagnetic interaction. The later correlation is supported by experiments. The magnetic properties of 1, 2, and three previously reported related compounds have been discussed in light of the structural parameters and also in light of the theoretical correlations determined here.