Photocatalytic Generation of Carbocation from Thiols and Application to Cross-Nucleophile Coupling.

Represented herein is a simple thiol identified as an effective precursor to photochemically form a carbocation. Thanks to the thiyl radical rapid transformation to disulfide, which serves not only to stabilize the generated thiyl radical but also to allow the second electron transfer to form a carbocation. The resulting carbocations, including primary benzylic, secondary, and tertiary carbocations, can smoothly couple with nitrogen, oxygen, and carbon nucleophilic coupling partners as well as complex drug molecules, accompanied by elemental sulfur formation in air.

Engineering Ultrathin CuxS Layer on Planar Sb2S3 Photocathode to Enhance Photoelectrochemical Transformation.

Sb2S3 has been extensively used as light absorber for photoelectrochemical cell. However, its p-type nature may result in the formation of Schottky junction with substrates, thus hindering the collection of photogenerated holes. Herein, an ultrathin CuxS layer is successfully engineered as the bottom junction for Sb2S3 for the first time. Capitalizing on its impressive electrical properties and superior optical properties, the CuxS layer exhibits a high work function of 4.90 eV, which causes the upward band bending of p-type Sb2S3, forming a hole-transparent structure with ohmic contact. The transparency of the ultrathin CuxS layer enables back-illumination of the Sb2S3/CuxS platform, facilitating the integration of intricate catalyst layers for photoelectrochemical transformation. When modified with Pt nanoparticles, the photocurrent density reaches -5.38 mA cm-2 at 0 V vs. RHE, marking a fourfold increase compared to the photocathode without CuxS layer. When introducing a molecular hybrid TC-CoPc@carbon black, a remarkable average photocurrent density of -0.44 mA cm-2 at the overpotential of 0 V is obtained for CO2 reduction reaction, while the photocurrent density is less than -0.03 mA cm-2 without CuxS.

Interfacial Charge Transfer Regulates Photoredox Catalysis.

Photoredox catalytic processes offer the potential for precise chemical reactions using light and materials. The central determinant is identified as interfacial charge transfer, which simultaneously engenders distinctive behavior in the overall reaction. An in-depth elucidation of the main mechanism and highlighting of the complexity of interfacial charge transfer can occur through both diffusive and direct transfer models, revealing its potential for sophisticated design in complex transformations. The fundamental photophysics uncover these comprehensive applications and offer a clue for future development. This research contributes to the growing body of knowledge on interfacial charge transfer in photoredox catalysis and sets the stage for further exploration of this fascinating area of research.

Photothermal Mineralization of Polyolefin Microplastics via TiO2 Hierarchical Porous Layer-Based Semiwetting Air-Plastic-Solid Interfaces.

Photo-mineralization of microplastics under mild conditions has emerged as a promising solution to plastic waste disposal. However, the inadequate contact between oxygen, water-insoluble polyolefin microplastics, and photocatalysts remains a critical issue. In this study, a TiO2 hierarchical porous layer (TiO2-HPL) photocatalyst is presented to establish air-plastic-solid triphase interfaces for the photothermal mineralization of polyolefins. The wettability of the TiO2-HPL-based triphase interface is finely controlled from plastophobic to plastophilic. High-resolution imaging and finite element simulation demonstrate the significance of a semiwetting state in achieving multidirectional oxygen diffusion through the hierarchical pore structure while maintaining sufficient contact between the plastic phase and photocatalysts. For low-density polyethylene, the TiO2-HPL achieves a photothermal mineralization rate of 5.63 mmol g-1 h-1 and a conversion of 26.3% after 20 h of continuous irradiation. Additionally, the triphase photocatalytic system with semiwetting gas-plastic-solid interfaces shows good universality for various polyolefin reagents and products, illustrating its potential in achieving efficient photothermal mineralization of non-degradable microplastics.

Concurrent Ammonia Synthesis and Alcohol Oxidation Boosted by Glutathione-Capped Quantum Dots under Visible Light.

Mother nature accomplishes efficient ammonia synthesis via cascade N2 oxidation by lightning strikes followed with enzyme-catalyzed nitrogen oxyanion (NOx -, x = 2,3) reduction. The protein environment of enzymatic centers for NOx --to-NH4 + process greatly inspires the design of glutathione-capped (GSH) quantum dots (QDs) for ammonia synthesis under visible light (440 nm) in tandem with plasma-enabled N2 oxidation. Mechanistic studies reveal that GSH induces positive shift of surface charge to strengthen the interaction between NOx - and QDs. Upon visible light irradiation of QDs, the balanced and rapid hole and electron transfer furnish GS·radicals for 2e-/2H+ alcohol oxidation and H·for 8e-/10H+ NO3 --to-NH4 + reduction simultaneously. For the first time, mmol-scale ammonia synthesis is realized with apparent quantum yields of 5.45% ± 0.64%, and gram-scale synthesis of value-added acetophenone and NH4Cl proceeds with 1:4 stoichiometry and stability, demonstrating promising multielectron and multiproton ammonia synthesis efficiency and sustainability with nature-inspired artificial photocatalysts.

Modular Synthesis of Improbable Rotaxanes with All-Benzene Scaffolds.

"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.

Surficial Host-Guest Responsive CsPbBr3 Perovskite Nanocrystals for Programmable Multi-Level Information Encryption.

The design of smart stimuli-responsive photoluminescent materials capable of multi-level encryption and complex information storage is highly sought after in the current information era. Here, a novel adamantyl-capped CsPbBr3 (AD-CsPbBr3 ) perovskite NCs, along with its supramolecular host-guest assembly partner a modified ß-CD (mCD), mCD@AD-CsPbBr3 , are designed and prepared. By dispersing these two materials in different solvents, namely, AD-CsPbBr3 in toluene, mCD@AD-CsPbBr3 in toluene, and mCD@AD-CsPbBr3 in methanol, the three solutions exhibit diverse photoluminescence (PL) turn-on/off or PL discoloration response upon supramolecular stimulus. Based on these responses, a proof-of-principle programmable Multi-Level Photoluminescence Encoding System (MPLES) is established. Three types of four-level and three types of three-level information encoding are achieved by the system. A layer-by-layer four-level information encryption and decryption as well as a two-level encrypted 3D code are successfully achieved.

A Conjugated Phenylene Nanocage with a Guest-Adaptive Deformable Cavity.

The highly strained, phenylene-derived organic cages are typically regarded as very rigid entities, yet their deformation potential and supramolecular properties remain underexplored. Herein, we report a pliable conjugated phenylene nanocage by synergistically merging rigid and flexible building blocks. The anisotropic cage molecule contains branched phenylene chains capped by a calix[6]arene moiety, the delicate conformational changes of which endow the cage with a remarkably deformable cavity. When complexing with fullerene guests, the cage showcases excellent guest-adaptivity, with its cavity volume capable of swelling by as much as 85 %.

Thiyl Radical Trapped by Cobalt Catalysis: An Approach to Markovnikov Thiol-Ene Reaction.

In the presence of a thiyl radical species, the catalytic Markovnikov thiol-ene reaction is challenging because it prefers to proceed via a radical pathway, thereby leading to anti-Markovnikov selectivity. In this work, a rare example of thiyl radical engaged in Markovnikov thiol-ene reaction enabled by cobalt catalysis is reported. This protocol features the avoidance of unique oxidants, exclusive regioselectivity, and broad substrate scope. Scalable synthesis and late-stage modification of complex molecules demonstrate the practicability of the protocol.

Assembly and Utility of a Drawstring-Mimetic Supramolecular Complex.

Inspired by the drawstring structure in daily life, here we report the development of a drawstring-mimetic supramolecular complex at the molecular scale. This complex consists of a rigid figure-of-eight macrocyclic host molecule and a flexible linear guest molecule which could interact through three-point non-covalent binding to form a highly selective and efficient host-guest assembly. The complex not only resembles the drawstring structure, but also mimics the properties of a drawstring with regard to deformations under external forces. The supramolecular drawstring can be utilized as an interlocked crosslinker for poly(methyl acrylate), and the corresponding polymer samples exhibit comprehensive enhancement of macroscopic mechanical performance including stiffness, strength, and toughness.

Regioselective Dearomative Amidoximation of Nonactivated Arenes Enabled by Photohomolytic Cleavage of N-nitrosamides.

Dearomative spirocyclization reactions represent a promising means to convert arenes into three-dimensional architectures; however, controlling the regioselectivity of radical dearomatization with nonactivated arenes to afford the spirocyclizative 1,2-difunctionalization other than its kinetically preferred 1,4-difunctionalization is exceptionally challenging. Here we disclose a novel strategy for dearomative 1,2- or 1,4-amidoximation of (hetero)arenes enabled by direct visible-light-induced homolysis of N-NO bonds of nitrosamides, giving rise to various highly regioselective amidoximated spirocycles that previously have been inaccessible or required elaborate synthetic efforts. The mechanism and origins of the observed regioselectivities were investigated by control experiments and density functional theory calculations.

Regioselective Diels-Alder Reactions of Anthracenes with Olefins via Visible Light Photocatalysis in a Homogeneous Solution.

Diels-Alder cycloaddition of anthracene with olefin is achieved in a homogeneous solution via energy transfer under visible light. A series of substrates including electroneutral styrene derivatives can be successfully converted into the corresponding cycloadducts in a head-to-head orientation with high to excellent yields. The high ortho-regioselectivity, mild condition, and broad substrate scope enable promising advances in organic transformation.

Photocatalytic redox-neutral selective single C(sp3)-F bond activation of perfluoroalkyl iminosulfides with alkenes and water.

Visible-light-promoted site-selective and direct C-F bond functionalization of polyfluorinated iminosulfides was accomplished with alkenes and water under redox-neutral conditions, affording a diverse array of γ-lactams with a fluoro- and perfluoroalkyl-substituted carbon centre. A variety of perfluoroalkyl units, including C2F5, C3F7, C4F9, and C5F11 underwent site-selective defluorofunctionalization. This protocol allows high chemoselectivity control and shows excellent functional group tolerance. Mechanistic studies reveal that the remarkable changes of the electron geometries during the defluorination widen the redox window between the substrates and the products and ensure the chemoselectivity of single C(sp3)-F bond cleavage.

A Smart Single-Fluorophore Polymer: Self-Assembly Shapechromic Multicolor Fluorescence and Erasable Ink.

A novel smart fluorescent polymer polyethyleneimine-grafted pyrene (PGP) is developed by incorporating four stimuli-triggers at molecular level. The triggers are amphiphilicity, supramolecular host-guest sites, pyrene fluorescence indicator, and reversible chelation sites. PGP exhibits smart deformation and shape-dependent fluorescence in response to external stimuli. It can deform into three typical shapes with a characteristic fluorescence color, namely, spherical core-shell micelles of cyan-green fluorescence, standard rectangular nanosheets of yellow fluorescence, and irregular branches of deep-blue fluorescence. A quasi-reversible deformation between the first two shapes can be dynamically manipulated. Moreover, driven by reversible coordination and the resulting intramolecular photoinduced electron transfer, PGP can be used as an aqueous fluorescence ink with erasable and recoverable properties. The fluorescent patterns printed by PGP ink on paper can be rapidly erased and recovered by simple spraying a sequence of Cu2+ and ethylene diamine tetraacetic acid aqueous solutions. This erase/recover transformation can be repeated multiple times on the same paper. The multiple stimulus responsiveness of PGP makes it have potential applications in nanorobots, sensing, information encryption, and anticounterfeiting.

Visible-Light-Mediated Generation of Acyl Radicals from Triazine Esters.

Acyl radicals are significant synthetic active species in organic synthesis. However, their generation via green and compatible methods remains challenging. Herein, we report an unprecedented visible-light-mediated approach for generating aryl acyl radicals from readily available triazine esters. This protocol with mild and redox-neutral conditions affords a diverse array of oxindoles attached to alcohol groups in a single operation. The recycling of leaving groups and a range of visible-light-mediated reactions using triazine ester as an acyl radical precursor demonstrate the synthetic potential of this methodology.

In situ assembly of nickel-based ultrathin catalyst film for water oxidation.

A nickel-based ultrathin catalyst film is assembled in situ from a solution of Ni(OAc)2 and a Schiff-base ligand L. The resulting ultrathin catalyst film shows a low overpotential of 330 mV, a steady current of 7 mA cm-2 for water oxidation over 10 h.

Amphiphilic Cobalt Phthalocyanine Boosts Carbon Dioxide Reduction.

Due to the easy accessibility, chemical stability, and structural tunability of the macrocyclic skeleton, cobalt phthalocyanines immobilized on carbon supports offer an ideal research model for advanced electrochemical carbon dioxide reduction reaction (eCO2 RR). In this work, an amphiphilic cobalt phthalocyanine (TC-CoPc) is loaded on multiwalled carbon nanotubes to reveal the roles of hydrophilic/hydrophobic properties on catalytic efficiency. Surprisingly, the resultant electrode exhibits a CO Faradaic efficiency (FECO ) of 95% for CO2 RR with turnover frequency (TOF) of 29.4 s-1 at an overpotential of 0.585 V over long-term electrolysis in a H-type cell. In the membrane electrode assembly (MEA) device, the boosted transport of water vapor to the catalyst layer slows down carbonate crystallization and enhances the stability of the electrode, with FECO value of >99% over 27 h at -0.25 A, representing the best selectivity and stability among reported molecular catalysts in MEA devices. The amphiphilic cobalt phthalocyanine, which decreases interfacial charge and mass transfer resistance and maintains effective contact between active sites and the electrolyte, highlights the exceptional CO2 conversion from a molecular perspective.

Tracking an FeV (O) Intermediate for Water Oxidation in Water.

High-valent iron-oxo species are appealing for conducting O-O bond formation for water oxidation reactions. However, their high reactivity poses a great challenge to the dissection of their chemical transformations. Herein, we introduce an electron-rich and oxidation-resistant ligand, 2-[(2,2'-bipyridin)-6-yl]propan-2-ol to stabilize such fleeting intermediates. Advanced spectroscopies and electrochemical studies demonstrate a high-valent FeV (O) species formation in water. Combining kinetic and oxygen isotope labelling experiments and organic reactions indicates that the FeV (O) species is responsible for O-O bond formation via water nucleophilic attack under the real catalytic water oxidation conditions.

Photothermal recycling of waste polyolefin plastics into liquid fuels with high selectivity under solvent-free conditions.

The widespread use of polyolefin plastics in modern societies generates huge amounts of plastic waste. With a view toward sustainability, researchers are now seeking novel and low-cost strategies for recycling and valorizing polyolefin plastics. Herein, we report the successful development of a photothermal catalytic recycling system for transforming polyolefin plastics into liquid/waxy fuels under concentrated sunlight or xenon lamp irradiation. Photothermal heating of a Ru/TiO2 catalyst to 200-300 °C in the presence of polyolefin plastics results in intimate catalyst-plastic contact and controllable hydrogenolysis of C-C and C-H bonds in the polymer chains (mediated by Ru sites). By optimizing the reaction temperature and pressure, the complete conversion of waste polyolefins into valuable liquid fuels (86% gasoline- and diesel-range hydrocarbons, C5-C21) is possible in short periods (3 h). This work demonstrates a simple and efficient strategy for recycling waste polyolefin plastics using abundant solar energy.

Amine-Free, Directing-Group-Free and Redox-Neutral α-Alkylation of Saturated Cyclic Ketones.

The activation of the α-C-H bond of ketones typically requires an amine and a directing group to guide the reaction selectivity in amine-catalysis carbonyl chemistry. For an α-C-H bond activation of ketone, directing groups are also required to control the reaction selectivity. Reported herein is the first α-alkylation of cyclic ketones in the absence of an amine catalyst and directing group. 1 H NMR, XPS, EPR studies and DFT calculations indicate that an α-carbon radical intermediate is formed through direct and selective activation of the inert α-C-H bond of ketones chelating on the surface of colloidal quantum dots (QDs). Such an interaction is essential for weakening the C-H bond, as exemplified, using CdSe QDs as the sole photocatalyst to execute α-C-H alkylation of cyclic ketones under visible-light irradiation. Without an amine catalyst and directing group, the high step- and atom-economy transformation under redox-neutral condition opens a new way for α-C-H functionalization of ketones in carbonyl chemistry.