Size Selectivity of a Copper Metal–Organic Framework and Origin of Catalytic Activity in Epoxide Alcoholysis

{Cu(bpy)(H₂O)₂(BF₄)₂(bpy)} (Cu‐MOF; MOF=metal–organic framework; bpy=4,4′‐bipyridine), with a 3D‐interpenetrated structure and saturated Cu coordination sites in the framework, possesses unexpectedly high activity in the ring‐opening reaction of epoxides with MeOH, although the reaction rate drops remarkably with more bulky alcohols. This (apparent) size selection and the single Cu²⁺ sites in an identical environment of the crystalline matrix resemble zeolites. The real nature of active sites was investigated by attenuated total reflection infrared (ATR‐IR), Raman, EPR, and UV/Vis spectroscopies. Cu‐MOF has highly dynamic structural properties that respond to MeOH; its framework dimensions change from 3D to 2D by restructuring to a symmetric coordination of four bpy units to Cu. This interaction is accompanied by the partial dissolution of Cu‐MOF as multi‐Cu clusters, in which Cu²⁺ ions are connected with bpy ligands. Although both molecular and surface catalysis contribute to the high rate of alcoholysis, the soluble oligomeric species (Cu_mbpy_n) are far more active. Finally, addition of diethyl ether to the reaction mixture induces the reconstruction of dissolved and solid Cu‐MOF to the original framework structure, thereby allowing excellent recyclability of Cu‐MOF as an apparent heterogeneous catalyst. In contrast, the original Cu‐MOF structure is maintained upon contact with larger alcohols, such as iPrOH and tBuOH, thus leading to poor activity in epoxide ring opening.     

The origin of chemo- and enantioselectivity in the hydrogenation of diketones on platinum

In the Pt-catalyzed hydrogenation of 1,1,1-trifluoro-2,4-diketones, addition of trace amounts of cinchonidine, O-methyl-cinchonidine, or (R,R)-pantoyl-naphthylethylamine induces up to 93% ee and enhances the chemoselectivity up to 100% in the hydrogenation of the activated carbonyl group to an OH function. A combined catalytic, NMR and FTIR spectroscopic, and theoretical study revealed that the two phenomena are coupled, offering the unique possibility for understanding the substrate-modifier-metal interactions. The high chemo- and enantioselectivities are attributed to the formation of an ion pair involving the protonated amine function of the chiral modifier and the enolate form of the substrate. DFT calculations including the simulation of the interaction of a protonated amine with the enolate adsorbed on a Pt 31 cluster revealed that only the C-O bond next to the CF3 group of the substrate is in direct contact with Pt and can be hydrogenated. The present study illustrates the fundamental role played by the metal surface and indicates that also the enol form can be the reactive species in the hydrogenation of the activated ketone on chirally modified Pt.     

Balayage Ping-Pong: A Convexity of Equilibrium Measures

In this paper we establish that the density of the equilibrium measure of finitely many intervals for both logarithmic and Riesz potentials is convex. The main tool is a balayage ping-pong technique. A?similar result is obtained for finitely many arcs on the unit circle. Applications to external field problems and constrained energy problems are presented.     

Reversible gas-phase redox processes catalyzed by Co-exchanged MFU-4l(arge)

Postsynthetic metal ion exchange in a benzotriazolate-based MFU-4l(arge) framework leads to a Co(II)-containing framework with open metal sites showing reversible gas-phase oxidation properties.     

Self-assembled one dimensional functionalized metal-organic nanotubes (MONTs) for proton conduction

Two self-assembled isostructural functionalized metal-organic nanotubes have been synthesized using 5-triazole isophthalic acid (5-TIA) with In(III) and Cd(II). In- and Cd-5TIA possess one-dimensional (1D) nanotubular architecture and show proton conductivity along regular 1D channels, measured as 5.35 × 10(-5) and 3.61 × 10(-3) S cm(-1) respectively.     

Classical and semirelativistic magnetohydrodynamics with anisotropic ion pressure

We study the magnetohydrodynamics (MHD) equations with anisotropic ion pressure and isotropic electron pressure under both the classical and semirelativistic approximations in order to develop a numerical model. The dispersion relation as well as the characteristic wave speeds are derived. In addition to the exact wave speed solutions, we also provide efficient approximate formulas for the semirelativistic magnetosonic speeds. The equations are discretized with the Rusanov and Harten-Lax-van Leer numerical schemes and implemented into the BATS-R-US MHD code. We perform a set of verification tests.     

Dynamics of a discrete population model for extinction and sustainability in ancient civilizations

We analyze a discrete version of a recently developed ratio dependent population-resource model. This model has been used to study the decline of the human and resource populations on Easter Island and the chaotic dynamics of moose and wolf populations in Canada. The dynamical system exhibits a rich behavior of fractal basins of attraction and a Neimark-Sacker bifurcation route to chaos. The model consists of a coupled pair of logistic equations, with the carrying capacity for the predators proportional to the number of prey.     

Sets with Interior Extremal Points for the Markoff Inequality

In this note we verify that for a set consisting of 3 intervals it is possible that the extreme value in the Markoff inequality occurs only at interior points.