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août 2023 – ChemDigest

Mois : août 2023

Ultra Robust and Highly Efficient Flexible Organic Solar Cells with Over 18 % Efficiency Realized by Incorporating a Linker Dimerized Acceptor

Ultra Robust and Highly Efficient Flexible Organic Solar Cells with Over 18 % Efficiency Realized by Incorporating a Linker Dimerized Acceptor

A linker dimer acceptor (DOY-TVT) was designed and synthesized. When incorporation of the DOY-TVT in D18:N3 system, the ductility and morphological stability of ternary blend films was successfully improved. A stabilized PCE of 18.06 % was obtained for flexible organic solar cells (f-OSCs) with ultrahigh mechanical robustness by incorporating DOY-TVT. Impressively, the optimal f-OSCs retain 97 % of the initial PCE even after 3000 bending cycles.

Abstract

The wearable application of flexible organic solar cells (f-OSCs) necessitates high power conversion efficiency (PCE) and mechanical robustness. However, photoactive films based on efficient non-fullerene small molecule acceptors (NF-SMAs) are typically brittle, leading to poor mechanical stability in devices. In this study, we achieved a remarkable PCE of 18.06 % in f-OSCs while maintaining ultrahigh mechanical robustness (with a crack-onset strain (COS) of higher than 11 %) by incorporating a linker dimerized acceptor (DOY-TVT). Compared to binary blends, ternary systems exhibit reduced non-radiative recombination, suppressed crystallization and diffusion of NF-SMAs, and improved load distribution across the chain networks, enabling the dissipation of the load energy. Thus, the ternary f-OSCs developed in this study achieved, high PCE and stability, surpassing binary OSCs. Moreover, the developed f-OSCs retained 97 % of the initial PCE even after 3000 bending cycles, indicating excellent mechanical stability (9.1 % higher than binary systems). Furthermore, the rigid device with inverted structure based on the optimal active layer exhibited a substantial increase in efficiency retention, with 89.6 % after 865 h at 85 °C and 93 % after more than 1300 h of shelf storage at 25 °C. These findings highlight the potential of the linker oligomer acceptor for realizing high-performing f-OSCs with ultrahigh mechanical robustness.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Wei Song, Qinrui Ye, Shuncheng Yang, Lin Xie, Yuanyuan Meng, Zhenyu Chen, Qun Gu, Daobin Yang, Jingyu Shi, Ziyi Ge
onlinelibrary.wiley.com/doi/10.1002/anie.202310034

Smart Emulsions Stabilized by a Multi‐headgroup Surfactant Tolerant to High Concentrations of Acids and Salts

Smart Emulsions Stabilized by a Multi-headgroup Surfactant Tolerant to High Concentrations of Acids and Salts

A multi-headgroup surfactant was synthesized that can be transformed among cationic (di-UAPAc), zwitterionic and bola structures by pH trigger. In strong acidity, di-UAPAc co-stabilizes OID emulsions in combination with silica particles which convert to Pickering emulsions upon addition of high concentration of salts.

Abstract

Retaining emulsions stable at high acidity and salinity is still a great challenge. Here, we report a novel multi-headgroup surfactant (C3H7−NH+(C10COOH)2, di-UAPAc) which can be reversibly transformed among cationic, anionic and zwitterionic forms upon pH variation. Stable oil-in-dispersion (OID) emulsions in strong acidity (pH=2) can be co-stabilized by low concentrations of di-UAPAc and silica nanoparticles. High salinity at pH=2 improves the adsorption of di-UAPAc on silica particles through hydrogen bonding, resulting in the transformation of OID emulsions into Pickering emulsions. Moreover, emulsification/demulsification and interconversion between OID and Pickering emulsions together with control of the viscosity and droplet size can be triggered by pH. The present work provides a new protocol for designing surfactants for various applications in harsh aqueous media, such as strong acidity and high salinity, involved in oil recovery and sewerage treatments.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Wanqing Zhang, Bernard P. Binks, Jianzhong Jiang, Zhenggang Cui
onlinelibrary.wiley.com/doi/10.1002/anie.202310743

Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances

Catalytic Synthesis of β-(Hetero)arylethylamines: Modern Strategies and Advances

This review provides a comprehensive overview of the recent progresses made in the catalytic synthesis of β-(hetero)arylethylamines, which have become widespread scaffolds in drug discovery. During the past decade, this field of research has expanded tremendously thanks to the development of enabling technologies such as C−H activation, photocatalysis, electrocatalysis, and organocatalysis, whose illustrative examples will be highlighted.

Abstract

β-(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum of biological properties, making them prime candidates for drug discovery. Conventional methods for their preparation often require engineered substrates that limit the flexibility of the synthetic routes and the diversity of compounds that can be accessed. Consequently, methods that provide rapid and versatile access to those scaffolds remain limited. To overcome these challenges, synthetic chemists have designed innovative and modular strategies to access the β-(hetero)arylethylamine motif, paving the way for their more extensive use in future pharmaceuticals. This review outlines recent progresses in the synthesis of (hetero)arylethylamines and emphasizes how these innovations have enabled new levels of molecular complexity, selectivity, and practicality.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Valentyn Pozhydaiev, Cyprien Muller, Joseph Moran, David Lebœuf
onlinelibrary.wiley.com/doi/10.1002/anie.202309289

Iridium‐Catalyzed Remote Site‐Switchable Hydroarylation of Alkenes Controlled by Ligands

Iridium-Catalyzed Remote Site-Switchable Hydroarylation of Alkenes Controlled by Ligands

An iridium-catalyzed remote site-switchable hydroarylation of alkenes controlled by two different ligands was reported. The protocol enables access to the products functionalized at the subterminal methylene and terminal methyl positions on an alkyl chain in good results. The results of the control experiments and DFT calculations demonstrate that the reaction involves a chain-walking process and the modified Chalk–Harrod-type mechanism.

Abstract

An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at the subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields and with good to excellent site-selectivities. The catalytic system showed good functional group tolerance and a broad substrate scope, including unactivated and activated alkenes. More importantly, the regioconvergent transformations of mixtures of isomeric alkenes were also successfully realized. The results of the mechanistic studies demonstrate that the reaction undergoes a chain-walking process to give an [Ar−Ir−H] complex of terminal alkene. The subsequent processes proceed through the modified Chalk–Harrod-type mechanism via the migratory insertion of terminal alkene into the Ir−C bond followed by C−H reductive elimination to afford the hydrofunctionalization products site-selectively.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Fei Li, Yicong Luo, Jinbao Ren, Qianjia Yuan, Deyue Yan, Wanbin Zhang
onlinelibrary.wiley.com/doi/10.1002/anie.202309859

A Bio‐Inspired Trehalose Additive for Reversible Zinc Anodes with Improved Stability and Kinetics

A Bio-Inspired Trehalose Additive for Reversible Zinc Anodes with Improved Stability and Kinetics

Trehalose (THL) is reported as electrolyte additive for the stabilization of zinc anodes. THL breaks the H-bond network of water and improves the interfacial reaction kinetics, realizing a stable and flat Zn deposition with exposure of the (002) plane. A highly reversible Zn anode was obtained, exhibiting a high CE of 99.8 % for 3000 cycles in Zn/Cu cells and a stable cycling for 1500 h under 9.0 % DOD in Zn symmetric cells.

Abstract

The moderate reversibility of Zn anodes, as a long-standing challenge in aqueous zinc-ion batteries, promotes the exploration of suitable electrolyte additives continuously. It is crucial to establish the absolute predominance of smooth deposition within multiple interfacial reactions for stable zinc anodes, including suppressing side parasitic reactions and facilitating Zn plating process. Trehalose catches our attention due to the reported mechanisms in sustaining biological stabilization. In this work, the inter-disciplinary application of trehalose is reported in the electrolyte modification for the first time. The pivotal roles of trehalose in suppressed hydrogen evolution and accelerated Zn deposition have been investigated based on the principles of thermodynamics as well as reaction kinetics. The electrodeposit changes from random accumulation of flakes to dense bulk with (002)-plane exposure due to the unlocked crystal-face oriented deposition with trehalose addition. As a result, the highly reversible Zn anode is obtained, exhibiting a high average CE of 99.8 % in the Zn/Cu cell and stable cycling over 1500 h under 9.0 % depth of discharge in the Zn symmetric cell. The designing principles and mechanism analysis in this study could serve as a source of inspiration in exploring novel additives for advanced Zn anodes.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Haoyu Li, Yu Ren, Yue Zhu, Jiaming Tian, Xinyi Sun, Chuanchao Sheng, Ping He, Shaohua Guo, Haoshen Zhou
onlinelibrary.wiley.com/doi/10.1002/anie.202310143

Carbonate Hydrogenated to Formate in the Aqueous Phase over Nickel/TiO2 Catalysts

Carbonate Hydrogenated to Formate in the Aqueous Phase over Nickel/TiO2 Catalysts

Carbonate hydrogenation to formate is a promising route to convert captured carbon dioxide into valuable chemicals. Developing inexpensive catalysts with high activity, selectivity, and stability remains challenging. The catalytic properties of nickel can be greatly changed through the regulation of the electronic structure by the support, which makes it possible to improve the catalytic performance.

Abstract

Carbonate hydrogenation to formate is a promising route to convert captured carbon dioxide into valuable chemicals, thus reducing carbon emissions and creating a revenue return. Developing inexpensive catalysts with high activity, selectivity, and stability remains challenging. We report a supported non-noble metal catalyst, Ni/TiO2, with great selectivity over 96 % and excellent stability in catalyzing the conversion of carbonate into formate in aqueous solution. Ni0 and Ni2+ species are both observed in Ni/TiO2 catalysts, and the synergistic effect of these two Ni components leads to high activity and high selectivity of carbonate hydrogenation to formate.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Xiaochen Zhang, Aowen Li, Haoyi Tang, Yao Xu, Xuetao Qin, Zheng Jiang, Qiaolin Yu, Wu Zhou, Liwei Chen, Meng Wang, Xi Liu, Ding Ma
onlinelibrary.wiley.com/doi/10.1002/anie.202307061

Size‐Selective Ionic Crosslinking Provides Stretchable Mixed Ionic–Electronic Conductors

Size-Selective Ionic Crosslinking Provides Stretchable Mixed Ionic–Electronic Conductors

Organic mixed ionic–electronic conductors (OMIECs) have been developed through the implementation of size-selective ionic crosslinking. The resulting OMIECs exhibit remarkable mechanical properties and high conductivity. These materials were utilized to fabricate stretchable thermoelectric generators, demonstrating excellent heat-to-electricity efficiency and high stability in humid environments.

Abstract

Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade-off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size-selective ionic crosslinking. This rationally designed crosslinking mediated by length-regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic–electronic conductivity in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Junwoo Lee, Hyunwoo Bark, Yazhen Xue, Pooi See Lee, Mingjiang Zhong
onlinelibrary.wiley.com/doi/10.1002/anie.202306994

Amination of Isonitriles in Water: Urea Synthesis under Biocompatible Conditions

Amination of Isonitriles in Water: Urea Synthesis under Biocompatible Conditions

Biocompatible ligation of isonitriles and amines to ureas in neutral aqueous medium was developed here. Direct labeling of Ac4GlcN has been achieved in Hep G2 cells, which may be used to diagnose proteins with abnormal expression in their native habitats. The ligation will provide new avenues for amines and isonitriles in chemical biology applications.

Abstract

Bioorthogonal reactions have been widely used to track biomolecules in living systems. Due to stringent requirements of physiological conditions, enriching the toolkit of bioorthogonal reactions remains the most important and challenging issue. Herein, the biocompatible ligation of isonitriles and amines to ureas in neutral aqueous medium was developed for the first time. The ligation showed benign nature of biocompatibility, broad substrate scope, and specific chemoselectivity. Meanwhile, urea as a natural linkage, its derivatives played an important role in medicinal chemistry. The second-order reaction rate constant (k2) was determined, which was higher or comparable to that of Staudinger ligation and strain-promoted azide-alkyne cycloaddition (SPAAC). Direct labeling of Ac4GlcN has been achieved in Hep G2 cells.

Wiley: European Journal of Organic Chemistry: Table of Contents
Authors: Qi Zhang, Xueting Wang, Shi‐Wu Chen, Meng Tang, Qian Zhang, Yiwen Xia
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202300779

Visible‐Light‐Mediated Synthesis of Bicalutamide by Regioselective Hydroxysulfonylation of Acrylamides

Visible-Light-Mediated Synthesis of Bicalutamide by Regioselective Hydroxysulfonylation of Acrylamides

Synthesis of anticancer drug bicalutamide promoted by visible light in one step from the corresponding N-arylacrylamide is described. This approach involves a one-pot hydroxysulfonylation reaction through a photocatalytic redox process. The use of Na2Eosin Y as photocatalyst and blue light allows the access to a broad range of α-hydroxysulfonylamides bearing a quaternary center in moderate to good yields with complete regioselectivity through radical process.

Abstract

Synthesis of anticancer drug bicalutamide promoted by visible light in one step from the corresponding N-arylacrylamide is described. This approach involves a one-pot hydroxysulfonylation reaction through a photocatalytic redox process. The use of Na2Eosin Y as photocatalyst and blue light allows the access to a broad range of α-hydroxysulfonylamides bearing a quaternary center in moderate to good yields with complete regioselectivity via radical process.

Wiley: European Journal of Organic Chemistry: Table of Contents
Authors: Mercedes Zurro, Sergio Torres‐Oya, Estíbaliz Merino
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202300535

Potassium Persulfate‐Glucose Mediated Synthesis of (3)‐S‐Arylthioindoles from Indole and Thiophenols in Water

Potassium Persulfate-Glucose Mediated Synthesis of (3)-S-Arylthioindoles from Indole and Thiophenols in Water

Synthesis of functionalized 3-(S)-arylthioindoles was achieved from indoles and aryl thiols. The coupling reaction was performed in water in the presence of K2S2O8 and glucose at room temperature.

Abstract

An efficient and eco-friendly method has been developed for the preparation of functionalized 3-(S)-arylthioindoles in good to excellent yields from indoles and aryl thiols in water. The coupling reaction was prompted by K2S2O8 in the presence of glucose at room temperature. Broad substrate scope, functional group tolerance, room temperature reactions and metal-free conditions are the salient features of the developed methodology.

Wiley: European Journal of Organic Chemistry: Table of Contents
Authors: Nitin Kumar, Rapelly Venkatesh, Sundaram Singh, Jeyakumar Kandasamy
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202300679

Catalyst‐Free [3+2] Cycloaddition of Isoquinolinium/Pyridinium Ylides and Electron‐Deficient Alkenes

Catalyst-Free [3+2] Cycloaddition of Isoquinolinium/Pyridinium Ylides and Electron-Deficient Alkenes

A mild and operationally simple one-pot protocol for the [3+2] cycloaddition of isoquinolinium/pyridinium ylides and electron-deficient alkenes using NaBH3CN as reductant has been developed. A series of pyrrolo[2,1-a]isoquinolines and pyrrolo[3,4-a]indolizines were synthesized in excellent yields (up to 99 %) with excellent diastereoselectivities (up to >20/1 dr).

Abstract

The development of simple-to-operate methods for the preparation of indolizidine derivatives are of great importance. A mild one-pot protocol for the [3+2] cycloaddition of isoquinolinium/pyridinium ylides and electron-deficient alkenes using NaBH3CN as reductant has been developed. The protocol has a broad substrate scope (more than 40 examples) and provides various novel hexahydroindolizidine derivatives in high yields and excellent diastereoselectivities (up to >20/1).

Wiley: European Journal of Organic Chemistry: Table of Contents
Authors: Xueting Zhou, Jun Shi, Jun‐Rong Song, Wei‐Dong Pan, Hai Ren, Wei Wu
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202300563

Photocatalytic C−H Functionalization of Nitrogen Heterocycles Mediated by a Redox Active Protecting Group

Photocatalytic C−H Functionalization of Nitrogen Heterocycles Mediated by a Redox Active Protecting Group

Herein, we report a photocatalytic strategy to efficiently access functionalized azaheterocycles starting from one equivalent of an heterocyclic precursor incorporating a redox active benzamide protecting group. Activation of the protecting group triggered an intramolecular 1,5-HAT leading to α-aminoradical intermediates that were engaged in Giese additions or radical cross couplings to respectively afford alkylated or arylated products.

Abstract

Herein, we report a photocatalytic strategy for the C−H functionalization of saturated azaheterocycles under mild conditions with only one equivalent of starting material. Our strategy is based on a redox active benzamide protecting group that is activated via a halogen-atom transfer (XAT) process to trigger the formation of an α-amino radical. This nucleophilic radical intermediate was then engaged in Giese additions and radical cross couplings to afford C−H alkylated and arylated products.

Wiley: European Journal of Organic Chemistry: Table of Contents
Authors: Marianela G. Pizzio, Ernesto G. Mata, Philippe Dauban, Tanguy Saget
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202300616

Enzyme‐Driven, Switchable Catalysis Based on Dynamic Self‐Assembly of Peptides

Enzyme-Driven, Switchable Catalysis Based on Dynamic Self-Assembly of Peptides

Inspired by the phosphorylation regulation of reactive sites of natural enzymes, this work focuses on the de novo design of peptide-based enzyme mimetics with switchable catalytic activity. The zipper-like four-ligand structure on the peptide/Cu assemblies is the catalytically active center, imparting these enzyme mimetics with remarkable activity and selectivity.

Abstract

Covalent regulatory systems of enzymes are widely used to modulate biological enzyme activities. Inspired by the regulation of reactive-site phosphorylation in organisms, we developed peptide-based catecholase mimetics with switchable catalytic activity and high selectivity through the co-assembly of nanofibers comprising peptides and copper ions (Cu2+). Through careful design and modification of the peptide backbone structure based on the change in the free energy of the system, we identified the peptide with the most effective reversible catalytic activity. Kinase/phosphatase switches were used to control the reversible transition of nanofiber formation and depolymerization, as well as to modulate the active-site microenvironment. Notably, the self-assembly and disassembly processes of nanofibers were simulated using coarse-grained molecular dynamics. Furthermore, theoretical calculations confirmed the coordination of the peptide and Cu2+, forming a zipper-like four-ligand structure at the catalytically active center of the nanofibers. Additionally, we conducted a comprehensive analysis of the catalytic mechanism. This study opens novel avenues for designing biomimetic enzymes with ordered structures and dynamic catalytic activities.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Qing Li, Jiwei Min, Jiaxing Zhang, Meital Reches, Yuhe Shen, Rongxin Su, Yuefei Wang, Wei Qi
onlinelibrary.wiley.com/doi/10.1002/anie.202309830

Chemodivergent Staudinger Reactions of Secondary Phosphine Oxides and Application to the Total Synthesis of LL–D05139β Potassium Salt

Chemodivergent Staudinger Reactions of Secondary Phosphine Oxides and Application to the Total Synthesis of LL–D05139β Potassium Salt

Unprecedented chemodivergent Staudinger reactions of secondary phosphine oxides (SPO) have been developed. Reagent-controlled 1- or 2-nitrogen atom exclusions from azides have been achieved. Conversion of a chiral SPO to a phosphinic amide was stereoretentive, and the potassium salt of natural product LL-D05139β was synthesized for the first time.

Abstract

Unprecedented Staudinger reaction modes of secondary phosphine oxides (SPO) and organic azides are herein disclosed. By the application of various additives, selective nitrogen atom exclusion from the azide group has been achieved. Chlorotrimethylsilane mediates a stereoretentive Staudinger reaction with a 2-N exclusion which provides a valuable method for the synthesis of phosphinic amides and can be considered complementary to the stereoinvertive Atherton–Todd reaction. Alternatively, a 1-N exclusion pathway is promoted by acetic acid to provide the corresponding diazo compound. The effectiveness of this protocol has been further demonstrated by the total synthesis of the diazo-containing natural product LL-D05139β, which was prepared as a potassium salt for the first time in 6 steps and 26.5 % overall yield.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Wenjun Luo, Fang Xu, Zhenguo Wang, Jiyan Pang, Zixu Wang, Zhixiu Sun, Aiyun Peng, Xiaohui Cao, Le Li
onlinelibrary.wiley.com/doi/10.1002/anie.202310118

Noncovalent Modification of Cycloparaphenylene by Catenane Formation Using an Active Metal Template Strategy

Noncovalent Modification of Cycloparaphenylene by Catenane Formation Using an Active Metal Template Strategy**

A CPP-bipyridine catenane, which consists of [9]CPP and a 2,2′-bipyridine macrocycle, has been synthesized by an active metal template strategy. Catalytic C−H borylation/cross-coupling and metal complexation at the bipyridine macrocycle moiety illustrated the efficient post-functionalization of the [9]CPP-bipyridine catenane. The structural and photophysical properties of the Ag complex of [9]CPP-bipyridine catenane were also studied.

Abstract

The active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π-conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π-conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application. However, most CPP modifications require early stage functionalization and the direct modification of CPPs is very limited. Herein, we report the synthesis of a catenane consisting of [9]CPP and a 2,2′-bipyridine macrocycle as a new CPP analogue that contains a reliable synthetic scaffold enabling diverse and concise post-modification. Following the AMT strategy, the [9]CPP-bipyridine catenane was successfully synthesized through Ni-mediated aryl-aryl coupling. Catalytic C−H borylation/cross-coupling and metal complexation of the bipyridine macrocycle moiety, an effective post-functionalization method, were also demonstrated with the [9]CPP-bipyridine catenane. Single-crystal X-ray structural analysis revealed that the [9]CPP-bipyridine catenane forms a tridentated complex with an Ag ion inside the CPP ring. This interaction significantly enhances the phosphorescence lifetime through improved intermolecular interactions.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Hisayasu Ishibashi, Manuel Rondelli, Hiroki Shudo, Takehisa Maekawa, Hideto Ito, Kiichi Mizukami, Nobuo Kimizuka, Akiko Yagi, Kenichiro Itami
onlinelibrary.wiley.com/doi/10.1002/anie.202310613

Quantum Nuclear Delocalization and its Rovibrational Fingerprints

Quantum Nuclear Delocalization and its Rovibrational Fingerprints

Protons microsolvated by helium atoms, HHe+ n, offer fascinating insights into rovibrational excitations of polyatomic van der Waals complexes subject to pronounced quantum nuclear delocalization effects. Using quasi-exact calculations, we unveil for HHe3+ how different vibrational excitations modify in characteristic ways the torus-like quantum delocalization of one He around the quasi-linear HHe2+ core known from the quantum ground state.

Abstract

Quantum mechanics dictates that nuclei must undergo some delocalization. In this work, emergence of quantum nuclear delocalization and its rovibrational fingerprints are discussed for the case of the van der Waals complex . The equilibrium structure of is planar and T-shaped, one He atom solvating the quasi-linear He−H+−He core. The dynamical structure of , in all of its bound states, is fundamentally different. As revealed by spatial distribution functions and nuclear densities, during the vibrations of the molecule the solvating He is not restricted to be in the plane defined by the instantaneously bent chomophore, but freely orbits the central proton, forming a three-dimensional torus around the chromophore. This quantum delocalization is observed for all vibrational states, the type of vibrational excitation being reflected in the topology of the nodal surfaces in the nuclear densities, showing, for example, that intramolecular bending involves excitation along the circumference of the torus.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Irén Simkó, Christoph Schran, Fabien Brieuc, Csaba Fábri, Oskar Asvany, Stephan Schlemmer, Dominik Marx, Attila G. Császár
onlinelibrary.wiley.com/doi/10.1002/anie.202306744

Selectivity Control of the Ligand Exchange at Carbon in α‐Metallated Ylides as a Route to Ketenyl Anions

Selectivity Control of the Ligand Exchange at Carbon in α-Metallated Ylides as a Route to Ketenyl Anions**

The carbonylation of metallated ylides was found to result in competing phosphine versus metal salt elimination. The selectivity can effectively be controlled to enable selective isolation of the tosyl-substituted ketenyl anion. Its cryptand complex featured the “naked” ketenyl anion [Ts−C=C=O] in the solid state, which exhibited an only slightly bent S−C−C linkage indicating a pronounced ynolate character.

Abstract

α-Metallated ylides have recently been reported to undergo phosphine by CO exchange at the ylidic carbon atom to form isolable ketenyl anions. Systematic studies on the tosyl-substituted yldiides, R3P=C(M)Ts (M=Li, Na, K), now reveal that carbonylation may lead to a competing metal salt (MTs) elimination. This side-reaction can be controlled by the choice of phosphine, metal cation, solvent and co-ligands, thus enabling the selective isolation of the ketenyl anion [Ts−CCO]M (2-M). Complexation of 2-Na by crown ether or cryptand allowed structure elucidation of the first free ketenyl anion [Ts−CCO], which showed an almost linear Ts−C−C linkage indicative for a pronounced ynolate character. However, DFT studies support a high charge at the ketenyl carbon atom, which is reflected in the selective carbon-centered reactivity. Overall, the present study provides important information on the selectivity control of ketenyl anion formation which will be crucial for future applications.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Felix Krischer, Mike Jörges, Tsz‐Fai Leung, Heidar Darmandeh, Viktoria H. Gessner
onlinelibrary.wiley.com/doi/10.1002/anie.202309629

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

The luminescence of Mn2+ is strongly affected by the ligand field. Usually only the metal-ligand distance is considered a tool to tune the ligand field strength in phosphors. Using Zn[B2(SO4)4] as a host, we show that electronic effects are an important alternative and lead to unusual orange luminescence of Mn2+.

Abstract

The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in, e.g., phosphor-converted white light-emitting diodes (pc-wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5–3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal-ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer-like borosulfate ligand in the Mn2+-containing solid solutions Zn1-xMn x[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow-band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn−O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal-ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Lukas M. Träger, Leonard C. Pasqualini, Hubert Huppertz, Jörn Bruns, Markus Suta
onlinelibrary.wiley.com/doi/10.1002/anie.202309212

Environment‐Responsive Peptide Dimers Bind and Stabilize Double‐Stranded RNA

Environment-Responsive Peptide Dimers Bind and Stabilize Double-Stranded RNA

RNA shows immense biomedical potential but applications are limited by its instability and poor cellular uptake. Herein, we present a general approach of reversibly binding peptide dimers that stabilize double-stranded RNA, protect it against degradation by nucleases and enhance cellular RNA uptake. Under reducing conditions peptide dimers monomerize thereby triggering a controlled release of RNA.

Abstract

Double-stranded RNAs (dsRNA) possess immense potential for biomedical applications. However, their therapeutic utility is limited by low stability and poor cellular uptake. Different strategies have been explored to enhance the stability of dsRNA, including the incorporation of modified nucleotides, and the use of diverse carrier systems. Nevertheless, these have not resulted in a broadly applicable approach thereby preventing the wide-spread application of dsRNA for therapeutic purposes. Herein, we report the design of dimeric stapled peptides based on the RNA-binding protein TAV2b. These dimers are obtained via disulfide formation and mimic the natural TAV2b assembly. They bind and stabilize dsRNA in the presence of serum, protecting it from degradation. In addition, peptide binding also promotes cellular uptake of dsRNA. Importantly, peptide dimers monomerize under reducing conditions which results in a loss of RNA binding. These findings highlight the potential of peptide-based RNA binders for the stabilization and protection of dsRNA, representing an appealing strategy towards the environment-triggered release of RNA. This can broaden the applicability of dsRNA, such as short interfering RNAs (siRNA), for therapeutic applications.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Niall M. McLoughlin, Marvin A. Albers, Estel Collado Camps, Jannik Paulus, Youri A. Ran, Saskia Neubacher, Sven Hennig, Roland Brock, Tom N. Grossmann
onlinelibrary.wiley.com/doi/10.1002/anie.202308028

Lukáš Grajciar

Lukáš Grajciar

“The most exciting thing about my research is that it works, i.e., that our machine learning potentials are general and robust enough to ‘discover’ new chemistry that we have not thought about beforehand, but which often makes a lot of sense a posteriori … I celebrate success by starting to think about what to do next.” Find out more about Lukáš Grajciar in his Introducing … Profile.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors:
onlinelibrary.wiley.com/doi/10.1002/anie.202311849

Fu‐Sen Liang

Fu-Sen Liang

“The greatest scientific advance of the next decade will be understanding the fundamental mechanism of aging and gaining the ability to manipulate it … If I could be granted a superpower, it would be time travel because I could witness all the exciting historical moments.” Find out more about Fu-Sen Liang in his Introducing … Profile.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors:
onlinelibrary.wiley.com/doi/10.1002/anie.202311918

Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines

Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines

A new metal-free photocatalytic approach for the direct conversion of N,N-difunctionalized anilines into formamides derivatives (up to 89 % yield) under mild operative conditions is described herein. In this reaction, graphitic carbon nitride (g-CN) acts as a robust and fully recyclable visible-light photocatalyst that was easily recovered and reused up to five times without any significant drop in yield.

Abstract

The use of graphitic carbon nitride (g-CN) for the photocatalytic radical formylation of anilines, which represents a more sustainable and attractive alternative to the currently used approaches, is reported herein. Our operationally simple method occurs under mild conditions, employing air as an oxidant. In particular, the chemistry is driven by the ability of g-CN to reach an electronically excited state upon visible-light absorption, which has a suitable potential energy to trigger the formation of reactive α-amino radical species from anilines. Mechanistic investigations also proved the key role of the g-CN to form reactive superoxide radicals from O2 via single electron transfer. Importantly, this photocatalytic transformation provides a variety of functionalized formamides (15 examples, up to 89 % yield).

Wiley: Chemistry – A European Journal: Table of Contents
Authors: Giuseppe Sportelli, Gaia Grando, Manuela Bevilacqua, Giacomo Filippini, Michele Melchionna, Paolo Fornasiero
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202301718

Hydrogen Bonded Dimer of an Alcohol with the Derived Carboxylic acid Triggering their Sorption by Nanoporous‐crystalline PPO Films

Hydrogen Bonded Dimer of an Alcohol with the Derived Carboxylic acid Triggering their Sorption by Nanoporous-crystalline PPO Films

Poly(2,6-dimethyl-1,4-phenylene) oxide (PPO) films do not absorb benzyl alcohol (BAL) and benzoic acid (BA) separately from dilute aqueous solutions while exhibiting selective uptake of a BAL/BA equimolar compound, if BA is obtained by oxidizing BAL. Quantitative FTIR evaluations and structural information indicate uptake of a BAL/BA hydrogen-bonded dimer in PPO intrahelical crystalline channels.

Abstract

Films exhibiting nanoporous-crystalline (NC) phases of poly(2,6-dimethyl-1,4-phenylene) oxide (PPO), which are highly effective to absorb apolar organic guest molecules, are also able to absorb polar molecules (like alcohols and carboxylic acids) but only from concentrated organic solutions. NC PPO films, which do not absorb alcohols and carboxylic acids from diluted aqueous solutions, exhibits a huge uptake (even above 30 wt %) of benzyl alcohol (BAL) and benzoic acid (BA), if BA is obtained by spontaneous room temperature oxidation of BAL in aqueous solution. This phenomenon is rationalized by an easy uptake, mainly by the PPO intrahelical crystalline empty channels, of a BAL/BA 1/1 hydrogen-bonded dimer. This huge uptake of BAL/BA dimer by NC PPO films, which is also fast for films exhibiting the orientation of the crystalline helices perpendicular to the film plane (c orientation), can be exploited for purification of water from BAL, when present in traces. High and fast sorption of a hydrogen bonded dimer and negligible sorption of the two separate compounds is possibly unprecedented for absorbent materials.

Wiley: Chemistry – A European Journal: Table of Contents
Authors: Baku Nagendra, Antonietta Cozzolino, Maria Rosaria Acocella, Christophe Daniel, Paola Rizzo, Gaetano Guerra
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202301441

Partial Deoxygenative CO Homocoupling by a Diiron Complex

Partial Deoxygenative CO Homocoupling by a Diiron Complex

A diiron of a bis(beta-diketiminate) cyclophane effects the partially deoxygenative homologation of two CO molecules by two sequential one-electron reduction and silylation reactions to generate a ketenylidene ligand. The ketenylidene can be readily released from the complex along with retention of the dinuclear metal construct.

Abstract

One route to address climate change is converting carbon dioxide to synthetic carbon-neutral fuels. Whereas carbon dioxide to CO conversion has precedent in homo- and heterogeneous catalysis, deoxygenative coupling of CO to products with C−C bonds—as in liquid fuels—remains challenging. Here, we report coupling of two CO molecules by a diiron complex. Reduction of Fe2(CO)2L (2), where L2− is a bis(β-diketiminate) cyclophane, gives [K(THF)5][Fe2(CO)2L] (3), which undergoes silylation to Fe2(CO)(COSiMe3)L (4). Subsequent C-OSiMe3 bond cleavage and C=C bond formation occurs upon reduction of 4, yielding Fe2(μ-CCO)L. CO derived ligands in this series mediate weak exchange interactions with the ketenylidene affording the smallest J value, with changes to local metal ion spin states and coupling schemes (ferro- vs. antiferromagnetism) based on DFT calculations, Mössbauer and EPR spectroscopy. Finally, reaction of 5 with KEt3BH or methanol releases the C2O2− ligand with retention of the diiron core

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Devender Singh, Brian J. Knight, Vincent J. Catalano, Ricardo García‐Serres, Vincent Maurel, Jean‐Marie Mouesca, Leslie J. Murray
onlinelibrary.wiley.com/doi/10.1002/anie.202308813

Balancing Interfacial Reactions through Regulating p‐Band Centers by an Indium Tin Oxide Protective Layer for Stable Zn Metal Anodes

Balancing Interfacial Reactions through Regulating p-Band Centers by an Indium Tin Oxide Protective Layer for Stable Zn Metal Anodes

A new principle of regulating p-band center of metal oxide protective layer to balance Zn adsorption energy and migration energy barrier for effective Zn anode with long lifetime and low overpotential.

Abstract

Metallic zinc (Zn) is considered as one of the most attractive anode materials for the post-lithium metal battery systems owing to the high theoretical capacity, low cost, and intrinsic safety. However, the Zn dendrites and parasitic side reaction impede its application. Herein, we propose a new principle of regulating p-band center of metal oxide protective coating to balance Zn adsorption energy and migration energy barrier for effective Zn deposition and stripping. Experimental results and theoretical calculations indicate that benefiting from the uniform zincophilic nucleation sites and fast Zn transport on indium tin oxide (ITO), highly stable and reversible Zn anode can be achieved. As a result, the I−Zn symmetrical cell achieves highly reversible Zn deposition/stripping with an extremely low overpotential of 9 mV and a superior lifespan over 4000 h. The Cu/I−Zn asymmetrical cell exhibits a long lifetime of over 4000 cycles with high average coulombic efficiency of 99.9 %. Furthermore, the assembled I−Zn/AC full cell exhibits an excellent lifetime for 70000 cycles with nearly 100 % capacity retention. This work provides a general strategy and new insight for the construction of efficient Zn anode protection layer.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Yahan Meng, Mingming Wang, Jingwen Xu, Kui Xu, Kai Zhang, Zehui Xie, Zhengxin Zhu, Weiping Wang, Pengfei Gao, Xiangyang Li, Wei Chen
onlinelibrary.wiley.com/doi/10.1002/anie.202308454