The kinetically controlled supramolecular homo- and heteropolymerization of BDTs (1a and 1b) and BODIPYs (2a and 2b), endowed with amido-ester flexible ethylene linkers, that prompt the formation of seven-membered, intramolecularly H-bonded pseudocycles retarding the supramolecular polymerization, is investigated experimentally showing a complex scenario for their assembly.

The synthesis of linear benzo[1,2-b:4,5-b’]dithiophenes (BDTs, 1a and 1b) and 4,4-difuoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs, 2a and 2b), featuring modified connectivity between the central linear core and peripheral side chains, is reported. The supramolecular polymerization of these systems under kinetic control has been investigated. All compounds studied can form seven-membered, hydrogen-bonded pseudocycles, which hinder the progression of supramolecular polymerization. Notably, we demonstrate that both the nature of the central core and the connectivity of the linker joining the BDT or BODIPY units to the solubilizing moieties significantly influence the self-assembly kinetics. Among these, only compound 2b supports a successful seeded supramolecular polymerization (SSP), enabling accelerated conversion from monomeric to aggregated species. Finally, leveraging the geometric and electronic complementarity between the BDT and BODIPY cores, we have explored the copolymerization processes of 1a + 2a and 1b + 2b. The VT-UV-Vis studies carried out with these mixtures reveal the interaction of these units. Finally the seeded co-assembly further corroborates the formation of supramolecular copolymers.

Direct air capture (DAC) of carbon dioxide (CO2) emerges as a key strategy for climate crisis mitigation. Redox-mediated electrochemical carbon capture offers a promising route for energy-efficient DAC. This perspective discusses recent advances in the field, highlighting key challenges, such as oxygen interference at low CO2 concentrations, and outlines future directions for scalable, sustainable electrochemically mediated DAC.

Anthropogenic emissions of previously sequestered carbon continue to disrupt the natural carbon cycle, driving atmospheric carbon dioxide (CO2) concentrations beyond 420 ppm. This has resulted in global temperatures rising beyond 1.5 °C above the pre-industrial level. Direct air capture (DAC) of CO2 has emerged as a complementary mitigation strategy. However, current DAC technologies are limited by the high energy requirements inherent to the thermal release of captured CO2, which are caused by the low thermodynamic efficiency of heat-driven processes, as constrained by Carnot principles. Redox-mediated electrochemical carbon capture (RMECC) offers a promising pathway to overcome these limitations. RMECC with DAC application remains in an early developmental stage and requires further optimization to enable energy-efficient, cost-effective, and scalable deployment. In this perspective the design of sorbents, electrolytes, and electrochemical cell configurations in the field of RMECC are discussed with an emphasis on sustainable approaches for the demands of DAC applications. The challenges arising from the atmospheric dilution of CO2 within the more abundant and disruptive competitor oxygen are highlighted as a critical factor influencing sorbent performance. Recent advancements in RMECC are reviewed, key challenges are identified, and future directions are outlined to accelerate electrochemically mediated DAC towards practical implementation.

A borrowing hydrogen strategy using an NHC-Ir(III) catalyst enables selective N-functionalization of unprotected amino sugars using alcohols as alkylating agents. The use of unprotected substrates avoids extra steps of protection/deprotection, minimizing waste generation. The method was applied to different unprotected amino sugars that contain the amino group at C2, C3, or C6, and give access to biodegradable surfactants in a single synthetic step.

A method for direct N-functionalization of unprotected amino sugars using alcohols as alkylating agents is presented. The method relies on an iridium-catalyzed hydrogen borrowing strategy, offering a direct and highly effective approach for modifying unprotected carbohydrates. This approach avoids the need for additional protection/deprotection steps, minimizing waste generation. Different amino sugars and a broad variety of alcohols can be employed, including long-chain aliphatic alcohols for the synthesis of sugar-based surfactants. A synthetic pathway for obtaining unprotected C6 amino sugars is also presented.

A copper-catalyzed borylative coupling of allenes with 1-trifluoromethyl alkenes is reported. The reaction selectively provides synthetically versatile borylated 1,1-difluoro-1,5-dienes that can be converted into a range of medicinally relevant fluorinated compounds. Mechanistic studies reveal a key role of the catalytically generated LiCl by assisting the oxidative addition of the trifluoromethyl alkene into the catalytic allylcopper species.

An N-heterocyclic carbene/Cu-catalyzed coupling of allenes, bis(pinacolato)diboron, and trifluoromethyl alkenes is reported. The method allows access to stereodefined borylated 1,1-difluoro-1,5-dienes with high levels of selectivity. The integration of a 1,5-diene scaffold with boron and fluorine functionalities makes these products versatile building blocks for the synthesis of structurally diverse and valuable organofluorine compounds such as gem-difluoroalkenes, difluoromethylene units, and alkenyl fluorides. Mechanistic studies and density functional theory calculations shed light on key mechanistic aspects of the catalytic process and suggest that the in situ generated LiCl is essential for the reaction by assisting the oxidative addition of the trifluoromethyl alkene to the catalytically generated allylcopper species. It is found that the polarization of the key CF bond induced upon binding to LiCl results in a significant decrease of destabilizing Pauli repulsion, which is translated into a remarkable reduction of the activation barrier of the oxidative addition step.

An acylation or alkylation of vinyl cyclopropanes, employing tetra-n-butylammonium decatungstate as the photocatalyst, leading allyl ketones or alkenes is presented. A diverse range of substrates were compatible with this protocol, while flow conditions were also developed and mechanistic studies were also performed.

Vinyl cyclopropanes are useful linchpins for the synthesis of more complex scaffolds. In this work, we present an acylation or alkylation protocol of donor–acceptor vinyl cyclopropanes, employing tetra-n-butylammonium decatungstate as the photocatalyst. In this novel photochemical protocol, the formation of allyl ketones or alkenes from vinyl cyclopropanes and aldehydes or alkanes is presented. A diverse range of substrates are compatible with this protocol as a plethora of aldehydes, aliphatic or aromatic, alkanes, and vinyl cyclopropanes, decorated with amides, esters, or other substituents, can be employed. The method was proven compatible and can be performed under flow conditions, while further manipulation of the desired products was also demonstrated. Mechanistic studies are also described, which complement the proposed mechanism.

In the family of Mn2+ complexes formed with pentadentate bispidine chelates, functional groups that do not interfere with metal coordination can play a significant role in enhancing kinetic inertness and proton relaxation efficacy.

Mn2+ bispidine complexes combine unprecedented kinetic inertness with high relaxivity and are under scrutiny as potential magnetic resonance imaging (MRI) probes. This study demonstrates that, beyond the rigid, preorganized bispidine structure and the first coordination sphere of the Mn2+ ion, peripheral functional groups also play a role in enhancing those kinetic and relaxation properties. Three pentadentate ligands have been designed, synthesized, and their Mn2+ complexes investigated in order to elucidate the effect of noncoordinating carboxylate and amine pendants on the bispidine scaffold. While thermodynamic stability is not influenced by these variations in the peripheral structure, kinetic inertness is increased two-threefold when the ligand bears both carboxylate and amine functions. The synergistic effect of these groups could be related to the formation of a relatively stable dinuclear MnLZn complex, which can slow down transmetallation with Zn2+, the most important competitor of Mn2+ in vivo. Water exchange rate on these monohydrated chelates remains unaffected by variations in the complex charge. On the other hand, the simultaneous presence of deprotonated carboxylate and protonated amine functions enhances proton relaxivity, likely via reorganization of the second sphere water shell. These insights into structure–activity relationships help fine-tune the safety and the efficacy of MRI agents based on Mn2+-bispidines.

This review systematically consolidates the structural and theoretical advances of strain engineering in key electrochemical reactions, establishing a comprehensive framework that connects strain-induced modifications in electronic structures and surface properties to catalytic performance optimization. This review will supply critical insights into strain effects, bridging theoretical advancements and experimental breakthroughs to guide rational catalyst design.

Transition metals serve as pivotal electrocatalysts dueto tunable electronic structures and adsorption properties. Strain modulation emerges as a powerful strategy to tailor their electronic configurations (e.g., d-band center, surface energy) and adsorption behaviors, thereby optimizing reaction kinetics, product selectivity, and durability in different electrochemical processes. This review summarizes structural and theoretical advances in strain engineering for key electrochemical reactions, including hydrogen evolution, oxygen reduction, and CO2 reduction. In particular, different crystal facets exhibit distinct electrocatalytic performances, which are closely associated with facet-dependent strain, as strain modulations vary significantly across different facets. These facet-dependent strain effects highlight the critical role of surface structure, while density functional theory calculations and experimental techniques (e.g., epitaxial growth, mechanical deformation) provide mechanistic insights. Current challenges in nanoscale strain control and future opportunities for efficient electrocatalyst design toward sustainable energy are also outlined. This review offers significant insights into strain engineering, opening more opportunities for developing catalysts that enhance sustainable energyapplications.

We report the first hemiindigo-based photopharmacological agents, acting as nanomolar human acetylcholinesterase inhibitors with isomer-specific bioactivity. These compounds combine efficient and fully reversible photoswitching in aqueous solution using visible light, with a very high stability of the metastable isomer in water, especially for N-methyl analogs, as rationalized by both theoretical modeling and crystallographic analysis.

While photopharmacology enables precise spatiotemporal control over drug activity, its widespread reliance on UV-responsive molecules often hinders preclinical and clinical advancements. Thus, alternative scaffolds can offer promising advantages over the commonly used azobenzene family. In this study, we introduce the first hemiindigo-based photopharmacological agents, which are capable of isomer-dependent human acetylcholinesterase inhibition in the nanomolar range. These hemiindigo photoswitches exhibit highly favorable properties: They are fully functional in aqueous medium with good photoisomerization quantum yields, respond exclusively to blue-to-orange visible light (415–590 nm), and maintain high stability in their metastable form, even in physiological buffers. Notably, indoxyl N-methylation emerged as a key structural feature for optimizing photophysical properties, as demonstrated through crystallography and a theoretical model describing the photochemical pathways governing photoisomerization. Overall, this study paves the way for broader exploration and future applications of the largely overlooked hemiindigo scaffold in photopharmacology.

With a little help… OH•••F intramolecular hydrogen bonding (HB) strongly reduces alcohol HB acidity, resulting in underestimation of predicted HB acidity based on the molecular Kenny electrostatic potential. In contrast, CF2H–OH intramolecular interaction causes a positive cooperative effect leading to HB acidity enhancement, as revealed by conformational Kenny parameter analysis.

Hydrogen bonding is the most important noncovalent interaction involved in molecular binding events. Herein, how γ-fluorination alters the hydrogen bond (HB)-donating capacities of aliphatic alcohol groups is described. Herein, it is shown that the increase in HB-donating capacity due to the fluorine electronegativity can be significantly attenuated by 6-membered F•••HO intramolecular HB (IMHB), to the point where even in acyclic structures a decrease in alcohol HB-donating capacity is observed. The correlation of experimental HB-donating capacities (pK AHY-scale) with an easily computed descriptor, the Kenny molecular electrostatic potential V α (r), is discussed. It is shown that F•••HO IMHB leads to a V α (r) reduction which, in the case of highly populated IMHB conformers, leads to an underestimation of HB-donating capacities. The use of conformational electrostatic potentials, however, was found to be very useful to describe OH•••F IMHB, as well as to explain variations in experimental alcohol HB-donating capacities. Notably, V α (r)-analysis allowed the identification of the importance of conformational equilibria in explaining HB-donating capacity variations of identical fluorohydrin motifs, and notably it also reveals a cooperative effect involving a difluoromethyl group (CF2H) on alcohol HB-donating capacity.

The CuH-catalyzed stereodivergent hydroamination through asymmetric desymmetrization of cyclobutenes has been achieved, yielding a range of trisubstituted aminocyclobutanes with excellent results. A series of subsequent transformations, including the first asymmetric synthesis of two pharmaceutically active molecules, have been realized, and density functional theory calculations have been employed to illustrate the origin of the stereodivergence of the reaction.

Enantioenriched multisubstituted aminocyclobutanes (ACBs) are prevalent in numerous promising drug candidates due to their favorable pharmacological attributes. However, the catalytic asymmetric synthesis of multisubstituted ACBs remains underdeveloped. To tackle this challenge, this article presents the CuH-catalyzed asymmetric hydroamination of cyclobutenes through a desymmetrization approach. This protocol efficiently yields a diverse array of trisubstituted ACBs with high yields and excellent diastereo, as well as enantioselectivities. Significantly, the diastereoselectivity of the reaction can be finely tuned by altering the ligand, thereby enabling the stereodivergent synthesis of related bioactive compounds. The practical utility of this method is further underscored by a series of subsequent transformations of the products, which include the first asymmetric synthesis of two pharmaceutically active molecules. Moreover, density functional theory calculations have been employed to elucidate the pivotal role of ligands in achieving the stereodivergence of the reaction.