The Indenyl Effect: Accelerated C−H Amidation of Arenes via Ind*RhIII Nitrene Transfer Catalysis**

Investigations into C−H amidation reactions catalysed by cationic half-sandwich d⁶ metal complexes revealed that the indenyl-derived catalyst [Ind*RhCl₂]₂ significantly accelerated the directed ortho C−H amidation of benzoyl silanes using 1,4,2-dioxazol-5-ones. Ring slippage involving a haptotropic η⁵ to η³ rearrangement of the indenyl complex proposedly enables ligand substitution at the metal centre to proceed via associative, rather than dissociative pathways, leading to significant rate and yield enhancements. Intriguingly, this phenomenon appears specific for C−H amidation reactions involving weakly coordinating carbonyl-based directing groups with no acceleration observed for the corresponding reactions involving strongly coordinating nitrogen-based directing groups.     

Monitoring Photoinduced Interparticle Chemical Communication In Situ

Monitoring interparticle chemical communication plays a critical role in the nanomaterial synthesis as this communication controls the final structure and stability of global nanoparticles (NPs). Yet most ensemble analytical techniques, which could only reveal average macroscopic information, are unable to elucidate NP-to-NP interactions. Herein, we employ stochastic collision electrochemistry to track the morphology transformation of Ag NPs in photochemical process at the single NP level. By further statistical analysis of time-resolved current transients, we quantitatively determine the dynamic chemical potential difference and interparticle communication between populations of large and small Ag NPs. The high sensitivity of stochastic collision electrochemistry enables the in situ investigation of chemical communication-dependent transformation kinetics of NPs in photochemical process, shedding light on designing nanomaterials.     

Engineering Heterogeneous Catalysis with Strong Metal–Support Interactions: Characterization,Theory and Manipulation

Strong metal–support interactions (SMSI) represent a classic yet fast-growing area in catalysis research. The SMSI phenomenon results in the encapsulation and stabilization of metal nanoparticles (NPs) with the support material that significantly impacts the catalytic performance through regulation of the interfacial interactions. Engineering SMSI provides a promising approach to steer catalytic performance in various chemical processes, which serves as an effective tool to tackle energy and environmental challenges. Our Minireview covers characterization, theory, catalytic activity, dependence on the catalytic structure and inducing environment of SMSI phenomena. By providing an overview and outlook on the cutting-edge techniques in this multidisciplinary research field, we not only want to provide insights into the further exploitation of SMSI in catalysis, but we also hope to inspire rational designs and characterization in the broad field of material science and physical chemistry.     

Controlled Annealing in Adaptive Multicomponent Gels

We use a pH-driven annealing process to convert between co-assembled and self-sorted networks in multicomponent gels. The initially formed gels at low pH are co-assembled, with the two components coexisting within the same self-assembled structures. We use an enzymatic approach to increase the pH, resulting in a gel-to-sol transition, followed by a hydrolysis to lower the pH once again. As the pH decreases, a self-sorted network is formed by a two-stage gelation process determined by the pK_a of each component. This approach can be expanded to layered systems to generate many varied systems by changing composition and rates of pH change, adapting their microstructure and so allowing access to a far greater range of morphologies and complexity than can be achieved in single component systems.     

Targeted Synthesis of Isomeric Naphthalene-Based 2D Kagome Covalent Organic Frameworks

Targeted synthesis of kagome ( kgm ) topologic 2D covalent organic frameworks remains challenging, presumably due to the severe dependence on building units and synthetic conditions. Herein, two isomeric “two-in-one” monomers with different lengths of substituted arms based on naphthalene core (p-Naph and m-Naph) are elaborately designed and utilized for the defined synthesis of isomeric kgm Naph-COFs. The two isomeric frameworks exhibit splendid crystallinity and showcase the same chemical composition and topologic structure with, however, different pore channels. Interestingly, C₆₀ is able to uniformly be encapsulated into the triangle channels of m-Naph-COF via in situ incorporation method, while not the isomeric p-Naph-COF, likely due to the different pore structures of the two isomeric COFs. The resulting stable C₆₀@m-Naph-COF composite exhibits much higher photoconductivity than the m-Naph-COF owing to charge transfer between the conjugated skeletons and C₆₀ guests.     

Enantioselective Synthesis of N−N Biaryl Atropisomers through Iridium(I)-Catalyzed C−H Alkylation with Acrylates

Enantioselective synthesis of N−N biaryl atropisomers is an emerging area but remains underexplored. The development of efficient synthesis of N−N biaryl atropisomers is in great demand. Herein, the construction of N−N biaryl atropisomers through iridium-catalyzed asymmetric C−H alkylation is reported for the first time. In the presence of readily available Ir precursor and Xyl-BINAP, a variety of axially chiral molecules based on indole-pyrrole skeleton were obtained in good yields (up to 98 %) with excellent enantioselectivity (up to 99 % ee). In addition, N−N bispyrrole atropisomers could also be synthesized in excellent yields and enantioselectivity. This method features perfect atom economy, wide substrate scope, and multifunctionalized products allowing diverse transformations.     

Transition Metal Catalysis in Living Cells: Progress,Challenges, and Novel Supramolecular Solutions

The importance of transition metal catalysis is exemplified by its wide range of applications, for example in the synthesis of chemicals, natural products, and pharmaceuticals. However, one relatively new application is for carrying out new-to-nature reactions inside living cells. The complex environment of a living cell is not welcoming to transition metal catalysts, as a diverse range of biological components have the potential to inhibit or deactivate the catalyst. Here we review the current progress in the field of transition metal catalysis, and evaluation of catalysis efficiency in living cells and under biological (relevant) conditions. Catalyst poisoning is a ubiquitous problem in this field, and we propose that future research into the development of physical and kinetic protection strategies may provide a route to improve the reactivity of catalysts in cells.     

Ruthenium-Catalyzed Activation of Nonpolar C−C Bonds via π-Coordination-Enabled Aromatization

Activation of C−C bonds allows editing of molecular skeletons, but methods for selective activation of nonpolar C−C bonds in the absence of a chelation effect or a driving force derived from opening of a strained ring are scarce. Herein, we report a method for ruthenium-catalyzed activation of nonpolar C−C bonds of pro-aromatic compounds by means of π-coordination-enabled aromatization. This method was effective for cleavage of C−C(alkyl) and C−C(aryl) bonds and for ring-opening of spirocyclic compounds, providing an array of benzene-ring-containing products. The isolation of a methyl ruthenium complex intermediate supports a mechanism involving ruthenium-mediated C−C bond cleavage.     

Visible-Light-Induced Control over Reversible Single-Chain Nanoparticle Folding

We introduce a class of single-chain nanoparticles (SCNPs) that respond to visible light (λ_max=415 nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester-bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (R_H). Importantly, the folding reaction and the light-induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.