The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

On lower iteration complexity bounds for the convex concave saddle point problems

Mathematical Programming - In this paper, we study the lower iteration complexity bounds for finding the saddle point of a strongly convex and strongly concave saddle point problem: $$\min _x\max...     

Spectroscopic properties of the low-lying electronic states and laser cooling feasibility for the SrI molecule

Laser cooling of a molecule with heavy nuclei is often complicated because of the density distribution of the electronic states. Here, we evaluate the feasibility of the laser cooling of the SrI molecule by calculating the potential energy curves and transition dipole moments of the ground and low-lying excited states using the multi-reference configuration interaction plus Davidson corrections (MRCI + Q) and the all-electron basis sets of ANO-RCC. The relativistic effect and the spin-orbit coupling splits are included, because both Sr and I are heavy atoms. Based on the obtained potential energy curves, we solve the Schrödinger equation of nuclear motion to determine the rovibrational energy levels and the Franck-Condon factors. The spectroscopic parameters are obtained by fitting the rovibrational energy levels with the Dunham expression. The radiation lifetimes, the Doppler and recoil temperatures between the X²Σ⁺ and the ²Π_1/2/²Π_3/2/B²Σ⁺ states are calculated. 5-color laser cooling schemes for the molecule are proposed, which can lead to the total effective Franck-Condon factors being 0.99983, 0.99979, and 0.99941 for the three transitions, respectively. All the obtained results suggest that the SrI molecule is a feasible candidate for laser cooling.     

Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

Fully asynchronous stochastic coordinate descent: a tight lower bound on the parallelism achieving linear speedup

Mathematical Programming - We seek tight bounds on the viable parallelism in asynchronous implementations of coordinate descent that achieves linear speedup. We focus on asynchronous coordinate...     

Stochastic chemo-physical-mechanical degradation analysis on hydrated cement under acidic environments

The accumulation of material degradation under contact with aggressive aqueous environments could lead to reduced structural reliability. In terms of hydrated cementitious materials, such interactions often result in the chemo-physical-mechanical (CPM) degradation, which represents a multiphysics process of high non-linearity and complexity. By further considering the inevitable uncertainties associated with both the materials and the serving conditions, solving such a process requires novel probabilistic approaches. This paper presents a stochastic chemo-physical-mechanical (SCPM) degradation analysis on the hydrated cement under acidic environment. The SCPM analysis consists of modelling the stochastic chemophysical degradation by finite element method, and assessing the mechanical deterioration through analytical micromechanics. The proposed modelling framework couples the conventional Monte Carlo Simulation with a novel support vector regression algorithm. The present method is able to not only address the detailed degradation mechanisms, but also ensure low computational costs for an accurate SCPM degradation assessment.     

Designing Covalent Organic Frameworks with a Tailored Ionic Interface for Ion Transport across One-Dimensional Channels

A strategy based on covalent organic frameworks for ultrafast ion transport involves designing an ionic interface to mediate ion motion. Electrolyte chains were integrated onto the walls of one-dimensional channels to construct ionic frameworks via pore surface engineering, so that the ionic interface can be systematically tuned at the desired composition and density. This strategy enables a quantitative correlation between interface and ion transport and unveils a full picture of managing ionic interface to achieve high-rate ion transport. Moreover, the effect of interfaces was scaled on ion transport; ion mobility is increased in an exponential mode with the ionic interface. This strategy not only sets a benchmark system but also offers a general guidance for designing ionic interface that is key to systems for energy conversion and storage.     

Formation of Azulene-Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction

Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.