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For the 2D metal‐free carbon catalysts, the atomic coplanar architecture enables a large number of pz orbitals to overlap laterally, thus forming π‐electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur‐doped defect‐rich graphitic carbon nitride (S‐Nv‐C3N4) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra‐thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long‐range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H2O2). Consequently, S‐Nv‐C3N4 exhibits high selectivity (>95 %) and achieves a superb H2O2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300 hour. According to theoretical calculation and in situ spectroscopy, the ortho‐S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process. [ABSTRACT FROM AUTHOR]

Expanding the diversity of multi‐macrocyclic nanocarbons, particularly those with all‐benzene scaffolds, represents intriguing yet challenging synthetic tasks. Complementary to the existing synthetic approaches, here we report an efficient and modular post‐functionalization strategy that employs iridium‐catalyzed C−H borylation of the highly strained meta‐cycloparaphenylenes (mCPPs) and an mCPP‐derived catenane. Based on the functionalized macrocyclic synthons, a number of novel all‐benzene topological structures including linear and cyclic chains, polycatenane, and pretzelane have been successfully prepared and characterized, thereby showcasing the synthetic utility and potential of the post‐functionalization strategy. [ABSTRACT FROM AUTHOR]

Visible‐light sensitive and bi‐functionally favored CO2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization of ultraviolet light and improve sluggish kinetics is demanded to conquer the current technique‐barrier of traditional Li‐CO2 battery. Here, a kind of redox molecular junction sp2c metal‐covalent organic framework (i.e. Cu3‐BTDE‐COF) has been prepared through the connection between Cu3 and BTDE and can serve as efficient photocathode catalyst in light‐assisted Li‐CO2 battery. Cu3‐BTDE‐COF with redox‐ability, visible‐light‐adsorption region, electron‐hole separation ability and endows the photocathode with excellent round‐trip efficiency (95.2 %) and an ultralow voltage hysteresis (0.18 V), outperforming the Schiff base COFs (i.e. Cu3‐BTDA‐COF and Cu3‐DT‐COF) and majority of the reported photocathode catalysts. Combined theoretical calculations with characterizations, Cu3‐BTDE‐COF with the integration of Cu3 centers, thiazole and cyano groups possess strong CO2 adsorption/activation and Li+ interaction/diffusion ability to boost the CRR/CER kinetics and related battery property. [ABSTRACT FROM AUTHOR]

"Improbable" rotaxanes consisting of interlocked conjugated components represent non‐trivial synthetic targets, not to mention those with all‐benzene scaffolds. Herein, a modular synthetic strategy has been established using an isolable azo‐linked pre‐rotaxane as the core module, in which the azo group functions as a tracelessly removable template to direct mechanical bond formations. Through versatile connections of the pre‐rotaxane and other customizable modules, [2]‐ and [3]rotaxanes derived from all‐benzene scaffolds have been accomplished, demonstrating the utility and potential of the synthetic design for all‐benzene interlocked supramolecules. [ABSTRACT FROM AUTHOR]

H2O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value‐added products. Here, a series of COFs (i.e. Cu3‐BT‐COF, Cu3‐pT‐COF and TFP‐BT‐COF) with regulated redox molecular junctions have been prepared to study H2O2 photosynthesis coupled with furfuryl alcohol (FFA) photo‐oxidation to furoic acid (FA). The FA generation efficiency of Cu3‐BT‐COF was found to be 575 mM g−1 (conversion ≈100 % and selectivity >99 %) and the H2O2 production rate can reach up to 187 000 μM g−1, which is much higher than Cu3‐pT‐COF, TFP‐BT‐COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H2O2 production and FFA photo‐oxidation to increase the efficiency. This is the first report about COFs for H2O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous‐crystalline catalysts in this field. [ABSTRACT FROM AUTHOR]

Metallic conductive 1T phase molybdenum sulfide (MoS2) has been identified as promising anode for sodium ion (Na+) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic‐interface engineering is employed for constructing 2H‐MoS2 layers assembled on single atomically dispersed Fe−N−C (SA Fe−N−C) anode material that boosts its reversible capacity. The work‐function‐driven‐electron transfer occurs from SA Fe−N−C to 2H‐MoS2 via the Fe−S bonds, which enhances the adsorption of Na+ by 2H‐MoS2, and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS2 with the ferromagnetic spin‐polarization of SA Fe−N−C occurs during the sodiation/desodiation process, which significantly enhances the Na+ storage kinetics, and thus the 1T/2H MoS2/SA Fe−N−C display a high electronic conductivity and a fast Na+ diffusion rate. [ABSTRACT FROM AUTHOR]

The full reaction photosynthesis of H2O2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H2O2. Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h−1 g−1) for H2O2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H2O2, which might extend the scope of COFs in H2O2 production. [ABSTRACT FROM AUTHOR]

The full reaction photosynthesis of H2O2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H2O2. Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h−1 g−1) for H2O2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H2O2, which might extend the scope of COFs in H2O2 production. [ABSTRACT FROM AUTHOR]

Phosphine‐mediated deoxygenative nucleophilic substitutions, such as the Mitsunobu reaction, are of great importance in organic synthesis. However, the conventional protocols require stoichiometric oxidants to trigger the formation of the oxyphosphonium intermediates for the subsequent nucleophilic additions. Through dual catalysis of photoredox and cobaloxime, we realized a radical strategy for the catalytic formation of acyloxyphosphonium ions that enables direct amidation. The deoxygenative protocol exhibits a broad scope and has been used in the late‐stage amidation of drug molecules. In addition to batch reactions, a continuous‐flow reactor was developed, enabling rapid peptide synthesis on gram scale. The successful assembly of a tetrapeptide on the solid support further demonstrated the versatility of this photocatalytic system. Moreover, experimental and computational studies are consistent with the hypothesis of acyloxyphosphonium ions being formed as the key intermediates. [ABSTRACT FROM AUTHOR]

In this work, we rationally designed a series of crystalline and stable dioxin‐linked metallophthalocyanine covalent organic frameworks (COFs; MPc‐TFPN COF, M=Ni, Co, Zn) under the guidance of reticular chemistry. As a novel single‐site catalysts (SSCs), NiPc/CoPc‐TFPN COF exhibited outstanding activity and selectivity for electrocatalytic CO2 reduction (ECR; Faradaic efficiency of CO (FECO)=99.8(±1.24) %/ 96.1(±1.25) % for NiPc/CoPc‐TFPN COF). More importantly, when coupled with light, the FECO and current density (jCO) were further improved across the applied potential range (−0.6 to −1.2 V vs. RHE) compared to the dark environment for NiPc‐TFPN COF (jCO increased from 14.1 to 17.5 A g−1 at −0.9 V; FECO reached up to ca. 100 % at −0.8 to −0.9 V). Furthermore, an in‐depth mechanism study was established by density functional theory (DFT) simulation and experimental characterization. For the first time, this work explored the application of COFs as photo‐coupled electrocatalysts to improve ECR efficiency, which showed the potential of using light‐sensitive COFs in the field of electrocatalysis. [ABSTRACT FROM AUTHOR]

Computational chemistry, peptides, phosphines, redox chemistry, visible-light chemistry Keywords: computational chemistry; peptides; phosphines; redox chemistry; visible-light chemistry EN computational chemistry peptides phosphines redox chemistry visible-light chemistry 1 1 1 01/20/22 20220126 NES 220126 B Amides are ubiquitous b in biological and medicinal chemistry. Inside Back Cover: Generation of Oxyphosphonium Ions by Photoredox/Cobaloxime Catalysis for Scalable Amide and Peptide Synthesis in Batch and Continuous-Flow (Angew. [Extracted from the article]