Mechanochromic Delayed Fluorescence Switching in Propeller-Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli-Responsive Intramolecular Charge-Transfer Excited States

Herein, the universal design of high-efficiency stimuli-responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli-triggered TADF switching for a series of carbazole–isophthalonitrile-based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X-ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited-state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light-emitting diodes using a single TADF emitter.     

Understanding and Controlling Fluorinated Diacyl Peroxides and Fluoroalkyl Radicals in Alkene Fluoroalkylations

The demand for practical methods for the synthesis of novel fluoroalkyl molecules is increasing owing to their diverse applications. Our group has achieved efficient difunctionalizing fluoroalkylations of alkenes using fluorinated carboxylic anhydrides as user-friendly fluoroalkyl sources. Fluorinated diacyl peroxide, prepared in situ from carboxylic anhydrides, enables the development of novel reactions when used as a radical fluoroalkylating reagent. In this account, we aim to provide an in-depth understanding of the structure, bonding, and reactivity of fluorinated diacyl peroxides and radicals as well as their control in fluoroalkylation reactions. In the first part of this account, the physical properties and reactivity of diacyl peroxides and fluoroalkyl radicals are described. In the subsequent part, we categorize the reactions into copper-catalyzed and metal-free methods utilizing the oxidizing properties of fluorinated diacyl peroxides. We also outline examples and mechanisms.     

Chiral Iodotriptycenes: Synthesis and Catalytic Applications

Invited for this month′s cover picture is the group of Thomas Wirth at Cardiff University (UK). The cover picture shows two structures of triptycenes. In each of these molecules all three aromatic rings are different with the rigid structure of the molecules making them chiral. The two sp³-carbons shown in red and green are the stereocentres with defined configuration. These molecules contain the crucial iodine functionality which are utilised to generate hypervalent iodine(III)-catalysts in situ . The authors acknowledge Dr. Yu Wang for the creation of the cover image. Read the full text of their Research Article at 10.1002/open.202200145 .     

Chemoselective N-acetylation of primary aliphatic amines promoted by pivalic or acetic acid using ethyl acetate as an acetyl donor

The combination of pivalic or acetic acid as a promoter and EtOAc as a solvent and acetyl donor proved to be efficient for the chemoselective N-acetylation of primary aliphatic amines to afford the corresponding acetamides. We developed a simple and convenient approach, which requires mild reaction conditions. Competitive inter- and intramolecular reactions between aliphatic amines, alcohols, and aromatic amines were examined, and chemoselectivity was achieved by adjusting the conditions of the reaction.     

Reproducing Kernels for Iterated Parabolic Operators on the Upper Half Space with Application to Polyharmonic Bergman Spaces

We consider parabolic operators of fractional order and their iterates on the upper half space of the euclidean space. We deal with Hilbert spaces of solutions of those parabolic equations. We shall show, in this note, the existence of reproducing kernels and give a formula by using their fundamental solutions. As an application, we also discuss the polyharmonic Bergman spaces and give their reproducing kernels by using the Poisson kernel on the upper half space.     

An efficient method for 3,4-dihydroisoquinolinium ion formation,leading to a facile introduction of nucleophiles

The ketene silyl acetal derived from ethyl 2-benzyltetrahydroisoquinoline-1-carboxylate undergoes a rapid oxidation reaction with N-bromosuccinimide to form 3,4-dihydroisoquinolinium ion, which reacts with Grignard reagents to give 1,1-disubstituted tetrahydroisoquinolines in good yields.     

Adsorption and separation behavior of strontium and yttrium using a silica-based bis(2-ethylhexyl) hydrogen phosphate adsorbent

Journal of Radioanalytical and Nuclear Chemistry - (HDEHP?+?Hexa)/SiO2-P, a silica-based adsorbent, was prepared and used to separate Y(III) from a mixed solution of Sr(II) and Y(III)....     

Neural network optimization of material composition of a functionally graded material plate at arbitrary temperature range and temperature rise

Summary A neural network model is applied to optimization problems of material compositions for a functionally graded material plate with arbitrarily distributed and continuously varied material properties in the thickness direction. Unsteady temperature distribution is evaluated by taking into account the bounds of the number of the layers. Thermal stress components for an infinite functionally graded material plate are formulated under traction-free mechanical conditions. As a numerical example, a plate composed of zirconium oxide and titanium alloy is considered. In the optimization problem of minimizing the thermal stress distribution, the numerical calculations are carried out making use of the neural network. The optimum material composition is determined by taking into account the effect of temperature-dependence of material properties. The results obtained by neural network and ordinary nonlinear programming method are compared. Received 3 March 1998; accepted for publication 22 May 1998