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Direct photocatalytic conversion of methane to value-added C 1 oxygenate with O 2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH 4 to HCHO. We propose the directional activation of O 2 on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward •OOH. The synchronously generated •OOH and •CH 3 radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol g cat -1  h -1 . This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH 4 photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand., (© 2024. The Author(s).)

With the resurgence of electrosynthesis in organic chemistry, there is a significant increase in the number of routes available for late-stage functionalization (LSF) of drugs. Electrosynthetic methods, which obviate the need for hazardous chemical oxidants or reductants, offer unprecedented control of reactions through the continuous variation of the applied potential and the possibility of combination with photochemical processes. This capability is a substantial advantage for performing electrochemical or photoelectrochemical LSF. Ultimately, these protocols are poised to become a vital component of the medicinal chemist's toolkit. In this review, we discuss electrochemical protocols that have been demonstrated to be applicable for the LSF of pharmaceutical drugs, their derivatives, and natural substrates. We present and analyze representative examples to illustrate the potential of electrochemistry or photoelectrochemistry for the LSF of valuable molecular scaffolds., (Copyright © 2024, Li et al.)

Photocatalytic molecular oxygen activation has emerged as a valuable tool for organic synthesis, environmental remediation and energy conversion. Most reported instances have relied on high-energy light sources. Herein, 9-fluorenone-functionalized porous organic polymers (POPs) were reported to enable red-light-excited photocatalysis for the organic oxygenation reaction. Notably, this modification extends the conjugated backbone, allowing the capture of lower-energy light. Incorporating ketone groups into POPs also facilitates charge separation and enhances carrier concentration, thereby promoting catalytic efficiency. The new POP photomaterials exhibit high activity for the direct α-oxygenation of N -substituted tetrahydroisoquinolines (THIQs) using O 2 as a green oxidant under 640 nm light irradiation, achieving high yield in short reaction times. Detailed mechanistic investigations clearly showed the role of oxygen and the photocatalyst. This work provides valuable insights into the potential of ketone-modified POPs for superior photocatalytic activation of molecular oxygen under low-energy light conditions., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu 13 (Nap) 3 (PPh 3 ) 7 H 10 (hereafter Cu 13 Nap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions. In comparison, the isostructural Cu 13 (DCBT) 3 (PPh 3 ) 7 H 10 (hereafter Cu 13 DCBT), stabilized by 2,4-dichlorobenzenethiolate (DCBT), yields only 28%, and other previously reported Cu NCs (Cu 28 , Cu 29 , Cu 45 , Cu 57 , and Cu 61 ) yield in the range of 6-18%. The introduction of naphthalene thiolate to the surface of Cu 13 NCs influences their electronic structure and charge transfer in the ligand shell, enhancing visible light absorption and catalytic performance. Density functional theory (DFT) and experimental evidence suggest that the reaction proceeds primarily through an energy transfer mechanism. The energy transfer pathway is uncommon in the context of previous reports for decarboxylative oxidation reactions. Our findings suggest that strategically manipulating ligands holds significant potential for creating composite active sites on atomically precise copper NCs, resulting in enhanced catalytic efficacy and selectivity across various challenging reactions.

Developing innovative methodologies for disulfide preparation is of importance in contemporary organic chemistry. Despite significant advancements in nickel-catalyzed reductive cross-coupling reactions for forming carbon-carbon and carbon-heteroatom bonds, the synthesis of S-S bonds remains a considerable challenge. In this context, we present a novel approach utilizing nickel catalysts for the reductive cross-coupling of thiosulfonates. This method operates under mild conditions, offering a convenient and efficient pathway to synthesize a wide range of both symmetrical and unsymmetrical disulfides from readily available, bench-stable thiosulfonates with exceptional selectivity. Notably, this approach is highly versatile, allowing for the late-stage modification of pharmaceuticals and the preparation of various targeted compounds. A comprehensive mechanistic investigation has been conducted to substantiate the proposed hypothesis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Bicyclo[1.1.1]pentane (BCP), recognized as a bioisostere for para-disubstituted benzene, has gained widespread interest in drug development due to its ability to enhance the physicochemical properties of pharmaceuticals. In this work, we introduce a photoinduced, halogen bonding-initiated, metal-free strategy for synthesizing various BCP derivatives. This method involves the generation of nucleophilic α-aminoalkyl radicals via halogen-bonding adducts. These undergo selective radical addition to [1.1.1]propellane, yielding electrophilic BCP radicals that subsequently participate in polarity-matched additions, culminating in the difunctionalization of bicyclopentane. The versatility and practicality of this metal-free approach are underscored by its broad substrate scope, which includes late-stage functionalization and a series of valuable transformations, all conducted under mild reaction conditions., (© 2024 Wiley‐VCH GmbH.)

Chemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure-performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high-electronegative F and N co-doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic-N (Py-N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential-limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential-limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER., (© 2024 Wiley‐VCH GmbH.)

Our study unveils a pioneering methodology that effectively distributes Pd species within a zeolitic imidazolate framework-8 (ZIF-8). We demonstrate that Pd can be encapsulated within ZIF-8 as atomically dispersed Pd species that function as an excited-state transition metal catalyst for promoting carbon-carbon (C-C) cross-couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250 °C, forming Pd metal nanoparticles encapsulated in ZIF-8. This catalyst shows high rates and selectivity for carbon dioxide hydrogenation to methanol under industrially relevant conditions (250 °C, 50 bar): 7.46 mol methanol  mol metal -1  h -1 and >99 %. Our results demonstrate the correlations of the catalyst structure with the performances at experimental and theoretical levels., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In alkaline water electrolysis and anion exchange membrane water electrolysis technologies, the hydrogen evolution reaction (HER) at the cathode is significantly constrained by a high energy barrier during the water dissociation step. This study employs a phase engineering strategy to construct heterostructures composed of crystalline Ni 4 W and amorphous WO x aiming to enhance catalytic performance in the HER under alkaline conditions. This work systematically modulates the oxidation states of W within the amorphous WO x of the heterostructure to adjust the electronic states of the phase boundary, the energy barriers associated with the water dissociation step, and the adsorption/desorption properties of intermediates during the alkaline HER process. The optimized catalyst, Ni 4 W/WO x -2, with a quasi-metallic state of W coordinated by a low oxygen content in amorphous WO x , demonstrates exceptional catalytic performance (22 mV@10 mA cm -2 ), outperforming commercial Pt/C (30 mV@10 mA cm -2 ). Furthermore, the operando X-ray absorption spectroscopy analysis and theoretical calculations reveal that the optimized W atoms in amorphous WO x serve as active sites for water dissociation and the nearby Ni atoms in crystalline Ni 4 W facilitated the release of H 2 . These findings provide valuable insights into designing efficient heterostructured materials for energy conversion., (© 2024 Wiley‐VCH GmbH.)

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu 45 (TBBT) 29 (TPP) 4 (C 4 H 11 N) 2 H 14 ] 2+ ( Cu 45 ) (TBBT: 4- tert -butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu 45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.

Extremophilic proteins are valuable in various fields, but their expression can be challenging in traditional hosts like Escherichia coli due to misfolding and aggregation. Haloferax volcanii ( H. volcanii ), a halophilic expression system, offers a solution. This study examined cleavable and non-cleavable purification tags at both the N- and C-termini when fused with the superfolder green fluorescent protein (sfGFP) in H. volcanii . Our findings reveal that an N-terminal 8xHis-tag or Strep-tag ® II significantly enhances protein production, purity, and yield in H. volcanii . Further experiments with mCherry and halophilic alcohol dehydrogenase (ADH) showed improved expression and purification yields when the 8xHis-tag or Strep-tag ® II was positioned at the C-terminus for mCherry and at the N-terminus for ADH. Co-positioning 8xHis-tag and Twin-Strep-tag ® at the N-terminus of sfGFP, mCherry, and ADH yielded significantly enhanced results. These findings highlight the importance of thoughtful purification tag design and selection in H. volcanii , providing valuable insights for improving protein production and purification with the potential to advance biotechnological applications., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2024 Karan, Renn, Allers and Rueping.)

Atomically precise copper nanoclusters (NCs) are an emerging class of nanomaterials for catalysis. Their versatile core-shell architecture opens the possibility of tailoring their catalytically active sites. Here, we introduce a core-shell copper nanocluster (CuNC), [Cu 29 (S t Bu) 13 Cl 5 (PPh 3 ) 4 H 10 ] t BuSO 3 (S t Bu: tert -butylthiol; PPh 3 : triphenylphosphine), Cu 29 NC, with multiple accessible active sites on its shell. We show that this nanocluster is a versatile catalyst for C-heteroatom bond formation (C-O, C-N, and C-S) with several advantages over previous Cu systems. When supported, the cluster can also be reused as a heterogeneous catalyst without losing its efficiency, making it a hybrid homogeneous and heterogeneous catalyst. We elucidated the atomic-level mechanism of the catalysis using density functional theory (DFT) calculations based on the single crystal structure. We found that the cooperative action of multiple neighboring active sites is essential for the catalyst's efficiency. The calculations also revealed that oxidative addition is the rate-limiting step that is facilitated by the neighboring active sites of the Cu 29 NC, which highlights a unique advantage of nanoclusters over traditional copper catalysts. Our results demonstrate the potential of nanoclusters for enabling the rational atomically precise design and investigation of multi-site catalysts.

We have developed a novel Ni-catalyzed reductive cross-coupling reaction of aryl bromides and alkyl iodides via a photoactive electron donor-acceptor (EDA) complex. This photo-induced process enables the efficient construction of C(sp 2 )-C(sp 3 ) bonds in the absence of an external photocatalyst. Electronically and structurally diverse aryl bromides, as well as secondary and primary alkyl iodides could undergo this transformation smoothly. Natural product derivatives were employed successfully, and UV-vis spectroscopy was utilized to gain mechanistic insight.

A new cross-coupling of trifluoromethyl arenes has been realized via multiphoton photoredox catalysis. Trifluoromethyl arenes were demonstrated to undergo selective mono-defluorinative alkylation under mild reaction conditions providing access to a series of valuable α,α-difluorobenzylic compounds. The reaction shows broad substrate scope and general functional group tolerance. In addition to the electron-deficient trifluoromethyl arenes that are easily reduced to the corresponding radical anion, more challenging electron-rich substrates were also successfully applied. Steady-State Stern-Volmer quenching studies indicated that the trifluoromethyl arenes were reduced by the multiphoton excited Ir-based photocatalyst., (© 2024 Wiley‐VCH GmbH.)

The development of an electrochemical cobalt catalyzed C-Cl bond activation at room temperature for the nucleophilic addition of aryl and vinyl chlorides to α-ketoamides is described. The overall method operates through an electrochemically induced low valent cobalt catalyst that oxidatively adds to aryl or vinyl chlorides affording medicinally important 3-hydroxy oxindole and 3-hydroxypyrrolidinone scaffolds. The development of an enantioselective version using a chiral pyrox ligand is also demonstrated.

Excited-state nickel-catalyzed C-N cross-coupling of aryl bromides with sodium azide enables the synthesis of diarylamines and primary anilines under mild reaction conditions. The oxidative addition of electron-rich aryl bromides with low-valent Ni under the photochemical conditions is endothermic. Herein, we demonstrate a light-mediated nickel-catalyzed reaction of electronically rich aryl bromides that yields diarylamines, while the reaction with electron-deficient aryl bromides gives access to anilines at room temperature.

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN 4 S 1 , where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts., Competing Interests: Competing interests statement:The authors declare no competing interest.

The development of metal complexes that function as both photocatalyst and cross-coupling catalyst remains a challenging research topic. So far, progress has been shown in palladium(0) excited-state transition metal catalysis for the construction of carbon-carbon bonds where the oxidative addition of alkyl/aryl halides to zero-valent palladium (Pd 0 ) is achievable at room temperature. In contrast, the analogous process with divalent palladium (Pd II ) is uphill and endothermic. For the first time, we report that divalent palladium can act as a light-absorbing species that undergoes double excitation to realize carbon-nitrogen (C-N) cross-couplings under air. Differently substituted aryl halides can be applied in the mild, and selective cross-coupling amination using palladium acetate as both photocatalyst and cross-coupling catalyst at room temperature. Density functional theory studies supported by mechanistic investigations provide insight into the reaction mechanism., (© 2023 Wiley-VCH GmbH.)

Hydrogen atom transfer (HAT) and photoredox dual catalysis provides a unique opportunity in organic synthesis, enabling the direct activation of C/Si/S-H bonds. However, the activation of O-H bonds of β,γ-unsaturated oximes poses a challenge due to their relatively high redox potential, which exceeds the oxidizing capacity of most currently developed photocatalysts. We here demonstrate that the combination of HAT and photoredox catalysis allows the activation of O-H bond of β,γ-unsaturated oximes. The strategy effectively addresses the oxime's high redox potential and offers a universal pathway for iminoxyl radical formation. Leveraging the versatility of this approach, a diverse array of valuable heterocycles have been synthesized with the use of different radical acceptors. Mechanistic studies confirm a HAT process for the O-H bond activation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This work presents a hydrothermal-based facile method for synthesizing ZnFe 2 O 4, whose size can be controlled with the concentration of sodium acetate used as a fuel and its physical changes at nanoscales when exposed to two different gases. The structural, morphological, compositional, and electronic properties of the synthesized samples are also presented in this paper. The crystal structure of the synthesized samples was determined using an X-ray Diffractometer (XRD). The results revealed fluctuations in the size, lattice parameter, and strain in the nanoparticles with increasing the concentration of sodium acetate. Field-Emission Scanning Electron Microscopy (FESEM) was used to determine synthesized materials' morphology and particle size. It revealed that the particles possessed approximately spherical morphology whose size decreased significantly with the increasing amount of sodium acetate. Transmission Electron Microscopy (TEM) was utilized to determine the structure, morphology, and elemental distributions in particles at the nanoscale, and it confirmed the findings of XRD and FESEM analyses. The high-resolution TEM (HRTEM) imaging analysis of the nanoparticles in our studied samples revealed that the particles predominantly possessed (001) type facets. X-ray photoelectron spectroscopy (XPS) and core-loss electron energy loss spectroscopy (EELS) showed an increasing fraction of Fe 2+ with the decreasing size of the particles in samples. The Brunauer, Emmett, and Tellers (BET) analysis of samples revealed a higher surface area as the particle size decreases. In addition, the determined surface area and pore size values are compared with the literature, and it was found that the synthesized materials are promising for gas-sensing applications. The ab initio calculations of the Density of States (DOS) and Band structure of (001) surface terminating ZnFe 2 O 4 were carried out using Quantum Espresso software to determine the bandgap of the synthesized samples. They were compared to their corresponding experimentally determined bandgap values and showed close agreement. Finally, in-situ TEM measurement was carried out on one of the four studied samples with robust properties using Ar and CO 2 as reference and target gases, respectively. It is concluded from the presented study that the size reduction of the ZnFe 2 O 4 nanoparticles (NPs) tunes the bandgap and provides more active sites due to a higher concentration of oxygen vacancies. The in-situ TEM showed us a nanoscale observation of the change in one of the crystal structure parameters. The d spacing of ZnFe 2 O 4 NPs showed a noticeable fluctuation, reaching more than 5% upon exposure to CO 2 and Ar gases., (© 2023. The Author(s).)

Photocatalytic selective C(sp 3 )-H activation/cross-coupling reactions are appealing in organic synthesis. In this manuscript, we describe the development of photoexcited-state Pd-catalyzed dehydrogenative β-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C-S cross-coupling processes at room temperature. The transformation can be achieved by the direct generation of two distinct Pd-radical hybrid species and their capability to promote two different reactivities from Pd(0) and aryl sulfonyl chlorides, allowing for the efficient conversion of readily available amines into stable sulfonyl-substituted enamines at room temperature. The in-depth experimental, computational, and transient optical spectroscopic study and catalytic applications of a dehydrogenative functionalization event provide evidence for both static and dynamic quenching, as well as inner-sphere and outer-sphere mechanisms., (© 2023. Springer Nature Limited.)

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu 58 H 20 PET 36 (PPh 3 ) 4 ] 2+ (Cu 58 ; PET: phenylethanethiolate; PPh 3 : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into the surface-defective analog [Cu 57 H 20 PET 36 (PPh 3 ) 4 ] + (Cu 57 ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu 57 . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu 58 , Cu 57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu 57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts., (© 2023 Wiley-VCH GmbH.)

Competing Interests: Conflict of interest The authors declare that they have no conflict of interest.

The difunctionalization of unsaturated bonds plays a vital role in the enrichment of molecular complexity. While various catalytic methods for alkene and alkyne difunctionalization have been developed in recent years, hetero-functionalization the introduction of two different atoms has been less explored. This is mainly due to the challenges associated with achieving high chemo-, regio-, and stereoselectivity, especially when adding two similar atoms from the same group across unsaturated bonds. In this study, we describe a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry. This new method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes. Various chlorosilanes as well as chlorogermans, and chlorostannanes can be successfully used in combination with aryl/alkyl-substituted 1,3-enynes and primary, secondary, and tertiary alkyl bromides in the electroreductive coupling., (© 2023 Wiley-VCH GmbH.)