ABSTRACT Solvent‐ and temperature‐dependent self‐assembly studies are often applied as alternatives to concentration‐dependent analysis of supramolecular polymerization. However, spectral changes due to (de)aggregation are overlaid by solvatochromic or thermochromic effects, respectively, that can have significant impacts on the fit analysis. Here, a non‐aggregating N , N ’‐2,6‐diisopropylphenyl‐substituted perylene bisimide (PBI) was studied in eleven solvents from 283 to 363 K, to acquire information on the impact of solvent and temperature on absorption properties. Subsequently, isodesmic aggregation of a PBI chromophore was studied in different solvent mixtures of toluene and 1,1,2,2‐tetrachloroethane, CHCl 3 , or 1,2‐dichlorobenzene, revealing that even small solvatochromic effects can significantly falsify data analysis, and derived thermodynamic parameters highly depend on the wavelengths chosen for data analysis. This wavelength‐dependency and deviation of fit results from concentration‐dependent reference values was also found in the temperature‐dependent study due to varying degrees of thermochromism at different wavelengths. Still, if evaluated carefully by proper selection of suitable wavelengths, both methods can give reasonable results. The present example serves to illustrate the accuracy one can expect from the different methods and the reliability of thermodynamic parameters from concentration‐, solvent‐, and temperature‐dependent UV–vis studies for one of the most studied dyes in the field of self‐assemblies and supramolecular polymers.
ABSTRACT Balancing mechanical toughness, environmental durability, sensing accuracy in hydrogel based flexible devices remains challenging. This paper reports a multifunctional hydrogel P(AM‐co‐SBMA)/CMCS‐IL, synthesized via free radical polymerization in [EMIM][BF 4 ]/H 2 O binary solvent system, natural polysaccharide CMCS as rigid reinforcing network, AM and zwitterionic SBMA for flexibility. The hydrogen bonds provide exceptional tensile properties, enduring 961% strain and 80% compressive strain without fracturing. It exhibits strong dehydration resistance, retaining 80% of its water content after 12 h in room temperature environment. When assembled into FSC, the device has high specific capacitance of 151.6 F g − 1 at 0.2 A g − 1 and energy density of 21.06 Wh kg − 1 at 200 W kg − 1 , while maintaining 76% capacitance retention after 8,000 cycles. Crucially, the FSC shows outstanding electrochemical stability across different bending (0° to 180°) and wide temperature range (−20°C to 60°C). Additionally, a flexible strain sensor based on the hydrogel features rapid electromechanical response (response and recovery times of 0.7 s and 0.6 s) and captures bending deformations and subtle muscle activities with high signal to noise ratios. This multifunctional electrolyte provides a key design strategy for integrating smart skins and flexible energy storage systems.
ABSTRACT The site‐selective incorporation of deuterium into biologically active molecules has emerged as a powerful strategy for tuning the absorption, distribution, metabolism, and excretion (ADME) properties of pharmaceuticals. Among various deuterated motifs, the d 3 ‐deuteromethyl (CD 3 ) group has gained particular attention as a privileged pharmacophore, highlighted by its presence in three of five deuterated drugs approved thus far. By uniting the beneficial “magic methyl effect” with the kinetic isotope effect imparted by deuterium, d 3 ‐deuteromethylation can effectively reduce metabolic liabilities while preserving biological activity, leading to improved pharmacokinetic performance and enhanced therapeutic potential. In recent years, the development of novel CD 3 ‐containing reagents, together with advances in photocatalytic and electrocatalytic methodologies, has enabled the efficient installation of CD 3 groups with high selectivity under mild conditions. In parallel, hydrogen–deuterium (H‐D) exchange strategies enable precise d 3 ‐deuteromethylation at specific sites (such as α‐thio C(sp 3 )─H bonds and benzylic C(sp 3 )─H bonds), providing a complementary approach to isotopic incorporation. This review summarizes the major advances in d 3 ‐deuteromethylation over the past five years (from 2021 to 2026), with a particular focus on the design of novel CD 3 reagents, the application of H‐D exchange strategy in d 3 ‐deuteromethylation, and the mechanistic principles underlying these transformations.
ABSTRACT An efficient asymmetric reductive homocoupling of isatin imines is developed with a chiral diboron template, affording the corresponding chiral vicinal diamines bearing 3,3′‐bisoxindole scaffolds in up to 90% yield and 99% ee. The reaction features mild conditions and is compatible with various substitution patterns, signifying the broad applicability of diboron‐participated [3,3]‐sigmatropic rearrangement for the first time on functionalized ketimines. The unstable nature of chiral vicinal diamine products bearing 3,3′‐bisoxindole scaffolds, which are prone to undergo retro‐Mannich reaction, complicates the reaction.
ABSTRACT The formation of carbon–carbon bonds is a cornerstone of organic synthesis, with the Hosomi‐Sakurai reaction serving as a powerful tool for introducing allyl groups to carbonyl compounds. Traditionally, this transformation relies on Lewis acid catalysis to activate the carbonyl substrate. Here, we report a solvent‐assisted, catalyst‐free Hosomi‐Sakurai reaction of aldehydes, providing a direct, atom‐economical and operationally simple route to allylated products under mild conditions at room temperature. This method exhibits broad substrate scope, including aromatic and aliphatic aldehydes, and proceeds with high chemoselectivity and functional group tolerance. Mechanistically, HFIP acts as a dual facilitator: it activates the aldehyde via hydrogen bonding, enhancing its electrophilicity, while simultaneously stabilizing the intermediate formed after allylsilane addition, thereby promoting the reaction and eliminating the need for external catalysts, additives, or Lewis acids.
