Spacer Conformation Induced Multiple Hydrogen Bonds in 2D Perovskite toward Highly Efficient Optoelectronic Devices.

Two-dimensional (2D) Dion-Jacobson (DJ) perovskites typically outperform Ruddlesden-Popper (RP) analogs in terms of photodetection (PD). However, the mechanism behind this enhanced performance remains elusive. Theoretical calculations for elucidating interlayer spacer conformation-induced multiple hydrogen bonds in 2D perovskite are presented, along with the synthesis of DPAPbBr4 (DPB) single crystals (SCs) and their PD properties under X-ray/ultraviolet (UV) excitation. The high-quality DPB SC enhances PD with exceptional photoresponse attributes, including a high on/off ratio (4.89 × 104), high responsivity (2.44 A W⁻1), along with large dynamic linear range (154 dB) and low detection limit (7.1 nW cm⁻2), which are currently the best results among 2D perovskite SC detectors, respectively. Importantly, high-resolution images are obtained under UV illumination with weak light levels. The SC X-ray detector exhibits a high sensitivity of 663 µC Gyair⁻1 cm-2 at 10 V and a detection limit of 1.44 µGyair s⁻1. This study explores 2D DJ perovskites for efficient and innovative optoelectronic applications.

Unveiling the Electrolyte Cations Dependent Kinetics on CoOOH-Catalyzed Oxygen Evolution Reaction.

The electrolyte cations-dependent kinetics have been widely observed in many fields of electrocatalysis, however, the exact mechanism of the influence on catalytic performance is still a controversial topic of considerable discussion. Herein, combined with operando X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), we verify that the electrolyte cations could intercalate into the layer of pristine CoOOH catalyst during the oxygen evolution reaction (OER) process, while the bigger cations lead to enlarged interlayer spacing and increased OER activity, following the order Cs+ >K+ >Na+ >Li+ . X-ray absorption spectroscopy (XAS), in situ Raman, in situ Ultraviolet-visible (UV/Vis) spectroscopy, in situ XAS spectroscopy, cyclic voltammetry (CV), and theoretical calculations reveal that the intercalation of electrolyte cations efficiently modify the oxidation states of Co by enlarging the Co-O bonds, which in turn enhance the d-band center of Co, optimize the adsorption strength of oxygen intermediates, facilitate the formation of OER active Co(IV) species, and reduce the energy barrier of the rate-determing step (RDS), thereby enhancing the OER activity. This work not only provides an informative picture to understand the complicated dependence of OER kinetics on electrolyte cations, but also sheds light on understanding the mechanism of other electrolyte cation-targeted electrocatalysis.

Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling.

Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl2bpy2 catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies. The solvent and ligand were found to be essential for the generation of catalytic active Co(I) species, among which acetonitrile and bipyridine ligand are resistant to the disproportionation events of Co(I). Investigations, based on Quick-X-Ray Absorption Fine Structure (Q-XAFS) spectroscopy, Electron Paramagnetic Resonance (EPR), IR allied with DFT calculations, allow comprehensive mechanistic insights that establish the structural information of the catalytic active cobalt species along with the whole catalytic Co(I)/Co(III) cycle. Moreover, the acetonitrile and bipyridine system can be further extended to the acylation, allylation, and benzylation of aryl zinc reagents, which present a broad substrate scope with a catalytic amount of Co salt. Overall, this work provides a basic mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions.

Promoting water formation in sulphate-functionalized Ru for efficient hydrogen oxidation reaction under alkaline electrolytes.

Improving the sluggish kinetics of the hydrogen oxidation reaction (HOR) under alkaline electrolytes plays a significant role in the practical application of alkaline polymer electrolyte fuel cells (APEFCs). Here we report a sulphate functionalized Ru catalyst (Ru-SO4) that exhibits remarkable electrocatalytic performance and stability toward alkaline HOR, with a mass activity of 1182.2 mA mgPGM-1, which is four-times higher than that of the pristine Ru catalyst. Theoretical calculations and experimental studies including in situ electrochemical impedance spectroscopy and in situ Raman spectroscopy demonstrate that the charge redistribution on the interface of Ru through sulphate functionalization could lead to optimized adsorption energies of hydrogen and hydroxide, together with facilitated H2 transfer through the inter Helmholtz plane and precisely tailored interfacial water molecules, contributing to a decreased energy barrier of the water formation step and enhanced HOR performance under alkaline electrolytes.

Enantioselective Assembly of Ferrocenes with Axial and Planar Chiralities via Palladium/Chiral Norbornene Cooperative Catalysis.

The preparation of ferrocenes with both axial and planar chiralities poses a considerable challenge. Herein, we report a strategy for the construction of both axial and planar chiralities in a ferrocene system via palladium/chiral norbornene (Pd/NBE*) cooperative catalysis. In this domino reaction, the first established axial chirality is dictated by Pd/NBE* cooperative catalysis, while the latter planar chirality is controlled by the preinstalled axial chirality through a unique axial-to-planar diastereoinduction process. This method exploits readily available ortho-ferrocene-tethered aryl iodides (16 examples) and the bulky 2,6-disubstituted aryl bromides (14 examples) as the starting materials. Five- to seven-membered benzo-fused ferrocenes with both axial and planar chiralities (32 examples) are obtained in one step with constantly high enantioselectivities (>99% e.e.) and diastereoselectivities (>19:1 d.r.).

Hydroxyl-Binding Energy-Induced Kinetic Gap Narrowing between Acidic and Alkaline Hydrogen Oxidation Reaction on Intermetallic Ru3 Sn7 Catalyst.

Developing highly efficient catalysts toward alkaline hydrogen oxidation reaction (HOR) and narrowing the kinetic gap between acidic and alkaline electrolytes are of great importance for the practical application of alkaline exchange membrane fuel cell . Herein, ordered Ru3 Sn7 /C intermetallic compound has been developed for the HOR under alkaline and acidic conditions. The authors demonstrate that the ordered intermetallic Ru3 Sn7 /C shows much enhanced HOR activity, stability, and CO-tolerance compared with its disordered RuSn solid solution alloy counterpart. More importantly, the authors find that the kinetic gap of HOR between acidic and alkaline media is significantly narrowed in the as-synthesized intermetallic Ru3 Sn7 /C catalysts. Combined experiment results and theoretical calculations, the authors understand that promoted hydroxyl-binding energy on Ru3 Sn7 /C derived from the intermetallic-induced strong electron interaction is responsible for the accelerated alkaline HOR performance and narrowed kinetic gap.

Unraveling the Structure and Reactivity Patterns of the Indole Radical Cation in Regioselective Electrochemical Oxidative Annulations.

Oxidation-induced strategy for inert chemical bond activation through highly active radical cation intermediate has exhibited unique reactivity. Understanding the structure and reactivity patterns of radical cation intermediates is crucial in the mechanistic study and will be beneficial for developing new reactions. In this work, the structure and properties of indole radical cations have been revealed using time-resolved transient absorption spectroscopy, in situ electrochemical UV-vis, and in situ electrochemical electron paramagnetic resonance (EPR) technique. Density functional theory (DFT) calculations were used to explain and predict the regioselectivity of several electrochemical oxidative indole annulations. Based on the understanding of the inherent properties of several indole radical cations, two different regioselective annulations of indoles have been successfully developed under electrochemical oxidation conditions. Varieties of furo[2,3-b]indolines and furo[3,2-b]indolines were synthesized in good yields with high regioselectivities. Our mechanistic insights into indole radical cations will promote the further development of oxidation-induced indole functionalizations.

Electrochemical dual-oxidation strategy enables access to α-chlorosulfoxides from sulfides.

Electrochemistry contributes a strong tool for the manufacture of molecules, addressing intractable challenges in synthetic chemistry by enabling innovative reaction pathways. Herein, a bifunctional reagent, aqueous hydrochloric acid, is used to establish an electrochemical selective dual-oxidation approach that gives access to α-chlorosulfoxides from sulfides. This strategy presents broad substrate scope, high diastereoselectivity, and regioselectivity. The late-stage modification of amino acids and pharmaceutical derivatives further highlights the utility. Furthermore, detailed mechanistic studies reveal that the key success for this selective chemical transformation is the dual-oxidation process at the anode. This electrochemical dual-oxidation strategy may have wide universality; we anticipate diverse applications of this protocol across the many fields of chemistry.

Synergistic passivation and stepped-dimensional perovskite analogs enable high-efficiency near-infrared light-emitting diodes.

Formamidinium lead iodide (FAPbI3) perovskites are promising emitters for near-infrared light-emitting diodes. However, their performance is still limited by defect-assisted nonradiative recombination and band offset-induced carrier aggregation at the interface. Herein, we introduce a couple of cadmium salts with acetate or halide anion into the FAPbI3 perovskite precursors to synergistically passivate the material defects and optimize the device band structure. Particularly, the perovskite analogs, containing zero-dimensional formamidinium cadmium iodide, one-dimensional δ-FAPbI3, two-dimensional FA2FAn-1PbnI3n+1, and three-dimensional α-FAPbI3, can be obtained in one pot and play a pivotal and positive role in energy transfer in the formamidinium iodide-rich lead-based perovskite films. As a result, the near-infrared FAPbI3-based devices deliver a maximum external quantum efficiency of 24.1% together with substantially improved operational stability. Combining our findings on defect passivation and energy transfer, we also achieve near-infrared light communication with device twins of light emitting and unprecedented self-driven detection.

From N-H Nitration to Controllable Aromatic Mononitration and Dinitration-The Discovery of a Versatile and Powerful N-Nitropyrazole Nitrating Reagent.

Nitroaromatics are tremendously valuable organic compounds with a long history of being used as pharmaceuticals, agrochemicals, and explosives as well as vital intermediates to a wide variety of chemicals. Consequently, the exploration of aromatic nitration has become an important endeavor in both academia and industry. Herein, we report the identification of a powerful nitrating reagent, 5-methyl-1,3-dinitro-1H-pyrazole, from the N-nitro-type reagent library constructed using a practical N-H nitration method. This nitrating reagent behaves as a controllable source of the nitronium ion, enabling mild and scalable nitration of a broad range of (hetero)arenes with good functional group tolerance. Of note, our nitration method could be controlled by manipulating the reaction conditions to furnish mononitrated or dinitrated product selectively. The value of this method in medicinal chemistry has been well established by its efficient late-stage C-H nitration of complex biorelevant molecules. Density functional theory (DFT) calculations and preliminary mechanistic studies reveal that the powerfulness and versatility of this nitrating reagent are due to the synergistic "nitro effect" and "methyl effect".

Selective radical cascade (4+2) annulation with olefins towards the synthesis of chroman derivatives via organo-photoredox catalysis.

Due to the importance of chroman frameworks in medicinal chemistry, the development of novel synthetic methods for these structures is gaining increasing interest of chemists. Reported here is a new (4 + 2) radical annulation approach for the construction of these functional six-membered frameworks via photocatalysis. Featuring mild reaction conditions, the protocol allows readily available N-hydroxyphthalimide esters and electron-deficient olefins to be converted into a wide range of valuable chromans in a highly selective manner. Moreover, the present strategy can be used in the late-stage functionalization of natural product derivatives and biologically active compounds, which demonstrated the potential application. This method is complementary to the traditional Diels-Alder [4 + 2] cycloaddition reaction of ortho-quinone methides and electron-rich dienophiles, since electron-deficient dienophiles were smoothly transformed into the desired chromans.

Electronic Modulation of Ru Nanosheet by d-d Orbital Coupling for Enhanced Hydrogen Oxidation Reaction in Alkaline Electrolytes.

The alkaline polymer electrolyte fuel cells (APEFCs) hold great promise for using nonnoble metal-based electrocatalysts toward the cathodic oxygen reduction reaction (ORR), but are hindered by the sluggish anodic hydrogen oxidation reaction (HOR) in alkaline electrolytes. Here, a strategy is reported to promote the alkaline HOR performance of Ru by incorporating 3d-transition metals (V, Fe, Co, and Ni), where the conduction band minimum (CBM) level of Ru can be rationally tailored through strong d-d orbital coupling. As expected, the obtained RuFe nanosheet exhibits outstanding HOR performance with the mass activity of 233.46 A gPGM -1 and 23-fold higher than the Ru catalyst, even threefold higher than the commercial Pt/C. APEFC employing this RuFe as anodic catalyst gives a peak power density of 1.2 W cm-2 , outperforming the documented Pt-free anodic catalyst-based APEFCs. Experimental results and density functional theory calculations suggest the enhanced OH-binding energy and reduced formation energy of water derived from the downshifted CBM level of Ru contribute to the enhanced HOR activity.

A Modular Approach for Diversity-Oriented Synthesis of 1,3-trans-Disubstituted Tetrahydroisoquinolines: Seven-Step Asymmetric Synthesis of Michellamines†B and C.

1,3-trans-Disubstituted tetrahydroisoquinoline (THIQ) is a common heterocyclic structural unit of naphthylisoquinoline alkaloids. The assembly of this structural unit is not trivial, which constitutes a substantial challenge in the total synthesis of naphthylisoquinoline alkaloids and related pharmaceuticals. Herein, we report a modular and convergent method for the rapid assembly of 1,3-trans-disubstituted THIQ frameworks through a three-component Catellani reaction and a AuI -catalyzed cyclization/reduction cascade. With widely available simple aryl iodides, aziridines and (triisopropylsilyl)acetylene as the building blocks, this method paves a practical way for the diversity-oriented synthesis of 1,3-trans-disubstituted THIQs. Based on this new method, concise syntheses of an analogue of the new drug mevidalen and four naphthylisoquinoline alkaloids have been accomplished, demonstrating the broad synthetic utility of this approach.

Exfoliation of MoS2 Nanosheets Enabled by a Redox-Potential-Matched Chemical Lithiation Reaction.

Ion intercalation assisted exfoliation is the oldest and most popular method for the scalable synthesis of molybdenum disulfide (MoS2) nanosheets. The commonly used organolithium reagents for Li+ intercalation are n-butyllithium (n-BuLi) and naphthalenide lithium (Nap-Li); however, the highly pyrophoric nature of n-BuLi and the overly reducing power of Nap-Li hinder their extensive application. Here, a novel organolithium reagent, pyrene lithium (Py-Li), which has intrinsic safe properties and a well-matched redox potential, is reported for the intercalation and exfoliation of MoS2. The redox potential of Py-Li (0.86 V vs Li+/Li) is located just between the intercalation (1.13 V) and decomposition (0.55 V) potentials of bulk MoS2, thus allowing precise Li+ intercalation to form a lamellar LiMoS2 compound without undesirable structural damage. The lithiation reaction can be accomplished within 1 h at room temperature and the exfoliated nanosheets are almost single layer. This method also offers the advantages of low cost, high repeatability, and ease in realizing large-scale production.

Enantioselective Nickel-Catalyzed Reductive Aryl/Alkenyl-Cyano Cyclization Coupling to All-Carbon Quaternary Stereocenters.

An enantioselective nickel-catalyzed intramolecular reductive cross-coupling of C(sp2) electrophiles and cyano groups is reported. Enantioenriched CN-containing all-carbon quaternary stereocenters are assembled by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of an organic reductant, (EtO)2MeSiH, is crucial to the enantioselectivity and reactivity. Applications of the method are demonstrated through the synthesis of bioactive molecules and their cyanated analogues and the total synthesis of the natural product diomuscinone. This study exhibits the potential of desymmetrizing reductive coupling strategies to access structurally rigid and synthetically versatile molecules from readily available starting materials.

Intermolecular Energy Gap-Induced Formation of High-Valent Cobalt Species in CoOOH Surface Layer on Cobalt Sulfides for Efficient Water Oxidation.

Transition metal-based electrocatalysts will undergo surface reconstruction to form active oxyhydroxide-based hybrids, which are regarded as the "true-catalysts" for the oxygen evolution reaction (OER). Much effort has been devoted to understanding the surface reconstruction, but little on identifying the origin of the enhanced performance derived from the substrate effect. Herein, we report the electrochemical synthesis of amorphous CoOOH layers on the surface of various cobalt sulfides (CoSα ), and identify that the reduced intermolecular energy gap (Δinter ) between the valence band maximum (VBM) of CoOOH and the conduction band minimum (CBM) of CoSα can accelerate the formation of OER-active high-valent Co4+ species. The combination of electrochemical and in situ spectroscopic approaches, including cyclic voltammetry (CV), operando electron paramagnetic resonance (EPR) and Raman, reveals that Co species in the CoOOH/Co9 S8 are more readily oxidized to CoO2 /Co9 S8 than in CoOOH and other CoOOH/CoSα . This work provides a new design principle for transition metal-based OER electrocatalysts.

Electrochemically selective double C(sp2)-X (X = S/Se, N) bond formation of isocyanides.

The construction of C(sp2)-X (X = B, N, O, Si, P, S, Se, etc.) bonds has drawn growing attention since heteroatomic compounds play a prominent role from biological to pharmaceutical sciences. The current study demonstrates the C(sp2)-S/Se and C(sp2)-N bond formation of one carbon of isocyanides with thiophenols or disulfides or diselenides and azazoles simultaneously. The reported findings could provide access to novel multiple isothioureas, especially hitherto rarely reported selenoureas. The protocol showed good atom-economy and step-economy with only hydrogen evolution and theoretical calculations accounted for the stereoselectivity of the products. Importantly, the electrochemical reaction could exclusively occur at the isocyano part regardless of the presence of susceptible radical acceptors, such as a broad range of arenes and alkynyl moieties, even alkenyl moieties.

Catalytic Synthesis of Atropisomeric o-Terphenyls with 1,2-Diaxes via Axial-to-Axial Diastereoinduction.

Herein, we report a modular and convergent strategy for the assembly of atropisomeric o-terphenyls with 1,2-diaxes via palladium/chiral norbornene cooperative catalysis and axial-to-axial diastereoinduction. Readily available aryl iodides, 2,6-substituted aryl bromides, and potassium aryl trifluoroborates are used as the building blocks, laying the foundation for diversity-oriented synthesis of these scaffolds (46 examples). Other features include the unique axial-to-axial diastereoinduction mode, construction of two axes in a single operation, and step economy. DFT calculations are performed to rationalize the axial-to-axial diastereoinduction process. Synthetic utilities of this method in preparation of atropisomeric oligophenyls, chiral catalysts, and ligands are demonstrated.

ß-Substituted Alkenyl Heteroarenes as Dipolarophiles in the Cu(I)-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylides Empowered by a Dual Activation Strategy: Stereoselectivity and Mechanistic Insight.

The catalytic asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides with various electron-deficient alkenes provide the most straightforward protocol for the preparation of enantioenriched pyrrolidines in organic synthesis. However, the employment of conjugated alkenyl heteroarenes as dipolarophiles in such protocols to afford a class of particularly important molecules in medicinal chemistry is still a great challenge. Herein, we report that various ß-substituted alkenyl heteroarenes, challenging internal alkene substrates without a strong electron-withdrawing substituent, were successfully employed as dipolarophiles for the first time in the Cu(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides. This reaction furnishes a large array of multistereogenic heterocycles incorporating both the biologically important pyrrolidine and heteroarene skeletons in good yields with exclusive diastereoselectivity and excellent enantioselectivity. Our extensive density functional theory (DFT) calculations proposed a working model to explain the origin of the stereochemical outcome and elucidated uncommon dual activation/coordination of both the dipole and dipolarophile substrates by the metal, in which a sterically bulky, rigid, and monodentate phosphoramidite ligand with triple-homoaxial chirality plays a pivotal role in providing an effective chiral pocket around the metal center, resulting in high enantioselectivity. The additional coordination of the heteroatom in the dipolarophile substrate to Cu is also critical for the exclusive diastereoselectivity and enhanced reactivity. Our calculations also predicted the reverse and high enantioinduction for the corresponding substrates with monocyclic heteroarenes as well as regiospecific cycloaddition to the less reactive internal C═C bond of one related dipolarophile diene substrate. Such unique steric effect-directed enantioswitching and coordination-directed regioselectivity were verified experimentally.