An η3‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex

Milling two equivalents of K[1,3‐(SiMe₃)₂C₃H₃] (=K[A′]) with MgX₂ (X=Cl, Br) produces the allyl complex [K₂MgA′₄] ( 1 ). Crystals grown from toluene are of the solvated species [((η⁶‐tol)K)₂MgA′₄] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η¹) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η³‐allyl configuration on Mg is energetically preferred over the η¹‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′₂}₂].     

Photoswitchable Sol–Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin‐Decorated Cu24L24 Metal–Organic Cages as Junctions

Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre‐irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu₂₄L₂₄ metal–organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this “polyMOC” material can be reversibly switched between Cu^II, Cu^I, and Cu⁰. The instability of the MOC junctions in the Cu^I and Cu⁰ states leads to network disassembly, forming Cu^I/Cu⁰ solutions, respectively, that are stable until re‐oxidation to Cu^II and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper‐catalyzed azide‐alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.     

Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.     

Conformational Panorama and Chirality Controlled Structure–Energy Relationship in a Chiral Carboxylic Acid Dimer

Chirality recognition in dimers of tetrahydro‐2‐furoic acid (THFA) was studied in a conformer‐specific manner using rotational spectroscopy and theoretical approaches. THFA shows a strong preference for the trans‐ over the cis‐COOH configuration. Two drastically different scenarios are possible for the detectable (THFA)₂: a kinetically preferred dimer bound by feeble interactions between two trans THFAs or a thermodynamically favored dimer with a double hydrogen‐bonded ring structure between two cis subunits. To identify the conformers responsible for the extremely dense rotational spectra observed, it was essential not only to locate several hundred homo/heterochiral (THFA)₂ minima in ab initio calculations but also to evaluate the energetic connectivities among the minima. The study further reveals an interesting chirality dependent structure–energy ordering relationship. A method for enantiomeric excess (ee) determination of THFA is presented using a recently proposed chiral self‐tag approach.     

Effect of Shear Displacement and Stress Changes on Fracture Hydraulic Aperture and Flow Anisotropy

Transport in Porous Media - Fluid flow in fractures has the potential to drastically change the economic, environmental, and safety risks associated with a subsurface operation. This work focuses...     

A data-based stability-preserving model order reduction method for hyperbolic partial differential equations

Nonlinear Dynamics - This paper proposes a data-based approach for model order reduction that preserves incremental stability properties. Existing data-based approaches do typically not preserve...     

Effect of power-law nonlinearity on ${ \mathcal P }{ \mathcal T }$-symmetric optical system with fourth-order diffraction

Gaussian-type soliton solutions of the nonlinear Schrödinger (NLS) equation with fourth order dispersion, and power law nonlinearity in the novel parity-time (${ \mathcal P }{ \mathcal T }$)-symmetric quartic Gaussian potential are derived analytically and numerically. The exact analytical expressions of the solutions are obtained in the first two-dimensional (1D and 2D) power law NLS equations. By means of the linear stability analysis, the effect of power law nonlinearity on the stability of Gauss type solitons in different nonlinear media is carried out. Numerical investigations do confirm the stability of our soliton solutions in both focusing and defocusing cases, specially around the propagation parameters.     

Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles

Nanoparticles of cobalt phosphide, CoP, have been prepared and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) under strongly acidic conditions (0.50 M H₂SO₄, pH 0.3). Uniform, multi‐faceted CoP nanoparticles were synthesized by reacting Co nanoparticles with trioctylphosphine. Electrodes comprised of CoP nanoparticles on a Ti support (2 mg cm^?2 mass loading) produced a cathodic current density of 20 mA cm^?2 at an overpotential of ?85 mV. The CoP/Ti electrodes were stable over 24 h of sustained hydrogen production in 0.50 M H₂SO₄. The activity was essentially unchanged after 400 cyclic voltammetric sweeps, suggesting long‐term viability under operating conditions. CoP is therefore amongst the most active, acid‐stable, earth‐abundant HER electrocatalysts reported to date.     

Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates

Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd₂(TP)₃(H₂O)₄(1), Er₂(TP)₃(H₂O)₄(2), Yb₂(TP)₃(H₂O)₂(3), Yb₂(TP)₃(H₂O)₆(4), and Yb₂(TP)₃(H₂O)₈·2H₂O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H₂O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.