Search

High efficiently photocatalytic CO2 reduction (CO2RR) into liquid fuels in pure water system remains challenged. Iron polyphthalocyanine (FePPc) with strong light harvesting, unique Fe‐N4 structure, abundant pores, and good stability could serve as a promising catalyst for CO2 photoreduction. To further improve the catalytic efficiency, herein, symmetry‐breaking Fe sites are constructed by coupling with atomically precise M1Ag24 (M=Ag, Au, Pt) series clusters. Especially, the introduction of Pt1Ag24 causes the most asymmetric charge distribution of Fe in FePPc (followed by Au1Ag24 and Ag25), leading to the favorable CO2 adsorption and activation. In addition, Pt1Ag24‐FePPc exhibits the most effective photogenerated carriers transfer and separation. As a result, Pt1Ag24‐FePPc shows the methanol/ethanol yield of 48.55/32.97 μmol ⋅ gcat−1 ⋅ h−1 in H2O‐CO2 system under visible light irradiation, ~1.65/1.25‐fold, 1.83/1.37‐fold, and 3.60/1.61‐fold higher than that of Au1Ag24‐FePPc, Ag25‐FePPc, and FePPc, respectively. This work provides a concept for precisely construction and regulation symmetry‐breaking sites of cluster‐based catalysts for effective CO2 conversion. [ABSTRACT FROM AUTHOR]

The engineering of tunable photoluminescence (PL) in single materials with a full‐spectrum emission represents a highly coveted objective but poses a formidable challenge. In this context, the realization of near‐full‐spectrum PL emission, spanning the visible light range from 424 to 620 nm, in a single‐component two‐dimensional (2D) hybrid lead halide perovskite, (ETA)2PbBr4 (ETA+=(HO)(CH2)2NH3+), is reported, achieved through high‐pressure treatment. A pressure‐induced phase transition occurs upon compression, transforming the crystal structure from an orthorhombic phase under ambient conditions to a monoclinic structure at high pressure. This phase transition driven by the adaptive and dynamic configuration changes of organic amine cations enables an effective and continuous narrowing of the band gap in this halide crystal. The hydrogen bonding interactions between inorganic layers and organic amine cations (N−H⋅⋅⋅Br and O−H⋅⋅⋅Br hydrogen bonds) efficiently modulate the organic amine cations penetration and the octahedral distortion. Consequently, this phenomenon induces a phase transition and results in red‐shifted PL emissions, leading to the near‐full‐spectrum emission. This work opens a possibility for achieving wide PL emissions with coverage across the visible light spectrum by employing high pressure in single halide perovskites. [ABSTRACT FROM AUTHOR]

The development of small organic molecules that can convert light energy into chemical energy to directly promote molecular transformation is of fundamental importance in chemical science. Herein, we report a zwitterionic acridinium amidate as a catalyst for the direct functionalization of aliphatic C−H bonds. This organic zwitterion absorbs visible light to generate the corresponding amidyl radical in the form of excited‐state triplet diradical with prominent reactivity for hydrogen atom transfer to facilitate C−H alkylation with a high turnover number. The experimental and theoretical investigations revealed that the noncovalent interactions between the anionic amidate nitrogen and a pertinent hydrogen‐bond donor, such as hexafluoroisopropanol, are crucial for ensuring the efficient generation of catalytically active species, thereby fully eliciting the distinct reactivity of the acridinium amidate as a photoinduced direct hydrogen atom transfer catalyst. [ABSTRACT FROM AUTHOR]

Acridine frameworks stand as pivotal architectural elements in pharmaceuticals and photocatalytic applications, owing to their chemical adaptability, biological activity, and unique excited‐state dynamics. Conventional synthetic routes often entail specialized starting materials, anaerobic or moisture‐free conditions, and elaborate multi‐stage manipulations for incorporating diverse functionalities. Herein, we present a convergent approach integrating photo‐excitation of readily available ortho‐alkyl nitroarenes with copper‐promoted cascade annulation. This innovative system enables an aerobic, one‐pot reaction of o‐alkyl nitroarenes with arylboronic acids, thereby streamlining the modular construction of a wide array of acridine derivatives with various functional groups. This encompasses symmetrical, unsymmetrical and polysubstituted varieties, some of which are otherwise exceptionally difficult to synthesize. Furthermore, it significantly improves the production of structurally varied acridinium salts, featuring enhanced photophysical properties, high excited state potentials (E*red=2.08–3.15 V), and exhibiting superior performance in intricate photoredox transformations. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and difficulty in waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a "persistent chemical," and Nafion, a widely utilized sulfonated FP for ion‐exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8‐h irradiation of 405‐nm LED light, and the turnover number of the C−F bond dissociation per NC was 17200. Furthermore, 81 % defluorination of Nafion was achieved for 24‐h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light‐induced ligand displacements and Auger‐induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine‐recycling society. [ABSTRACT FROM AUTHOR]

Photocatalysis holds a pivotal position in modern organic synthesis, capable of inducing novel reactivities under mild and environmentally friendly reaction conditions. However, the merger of photocatalysis and transition‐metal‐catalyzed asymmetric C−H activation as an efficient and sustainable method for the construction of chiral molecules remains elusive and challenging. Herein, we develop a cobalt‐catalyzed enantioselective C−H activation reaction enabled by visible‐light photoredox catalysis, providing a synergistic catalytic strategy for the asymmetric dearomatization of indoles with high levels of enantioselectivity (96 % to >99 % ee). Mechanistic studies indicate that the excited photocatalyst was quenched by divalent cobalt species in the presence of Salox ligand, leading to the formation of catalytically active chiral Co(III) complex. Moreover, stoichiometric reactions of cobaltacycle intermediate with indole suggest that the irradiation of visible light also play a critical role in the dearomatization step. [ABSTRACT FROM AUTHOR]

A synergetic interaction between two or more photochromic chromophores has a potential to achieve advanced photochemical properties beyond conventional photochromic molecules and to realize photochemical control of complex systems using only a single molecule. Herein, we report a hybrid photochromic molecule consisting of hexaarylbiimidazole (HABI) and terarylene that exhibits multi‐state photochromism. The biphotochrome hybrid shows four‐state photochromic reaction involving sequentially proceeding photoreactions. The UV or visible light irradiation to the biphotochrome leads to the C−N bond breaking reaction of the HABI in preference to the ring‐closing reaction of the 6π‐electron system in the terarylene unit, leading to two terarylene radical molecules. The photogenerated terarylene radical further exhibits the 6π‐electrocyclization reaction by UV irradiation. The delocalized π‐radical on the closed‐ring form of the terarylene is efficient to enhance the photosensitivity to the NIR−I and ‐II region. Furthermore, a recombination reaction of radicals between the open‐ and closed‐ring isomers of terarylene affords an unprecedented photochromic dimer as a structural isomer of the initial molecule. This is a consequence of the sequential hybrid photochromic system involving the HABI and terarylene units. [ABSTRACT FROM AUTHOR]

Extremely limited research exploring the photocatalytic potential of main group metals, such as aluminum, gallium, and tin, has been undertaken due to their weak light harvesting properties. This study reports the efficient transformation of sugars to 5‐hydroxymethylfurfural (HMF) with high yield employing an original heterogeneous photocatalyst comprising a gallium(III) complex immobilized on an alumina support. Under visible light irradiation, the reaction rate of HMF formation is ~143 times higher than the equivalent thermal reaction performed in the absence of light. The turnover number (TON) of the heterogeneous gallium(III) photocatalyst was as high as 1500, which was ca. two orders of magnitude higher than the TON of the homogeneous gallium(III) system. It is proposed that photoirradiation significantly enhances the Lewis acidity of the catalyst by forming a semi‐coordination state between gallium(III) and N‐donor ligands, enabling the increased interaction of reactant sugar molecules with gallium(III) active sites. Consistent with this, the photoresponsive coordination of the gallium(III) complex and the abstraction of the hydroxy group by the metal under irradiation with visible light is observed by NMR spectroscopy for the first time. These findings demonstrate that efficient photocatalysts derived from the main group elements can facilitate biomass conversion using visible light. [ABSTRACT FROM AUTHOR]

Phosphorene and fullerene are representative two‐dimensional (2D) and zero‐dimensional (0D) nanomaterials respectively, constructing their heterodimensional hybrid not only complements their physiochemical properties but also extends their applications via synergistic interactions. This is however challenging because of their diversities in dimension and chemical reactivity, and theoretical studies predicted that it is improbable to directly bond C60 onto the surface of phosphorene due to their strong repulsion. Here, we develop a facile electrosynthesis method to synthesize the first phosphorene‐fullerene hybrid featuring fullerene surface bonding via P−C bonds. Few‐layer black phosphorus nanosheets (BPNSs) obtained from electrochemical exfoliation react with C602− dianion prepared by electroreduction of C60, fulfilling formation of the "improbable" phosphorene‐fullerene hybrid (BPNS‐s‐C60). Theoretical results reveal that the energy barrier for formation of [BPNS‐s‐C60]2− intermediate is significantly decreased by 1.88 eV, followed by an oxidization reaction to generate neutral BPNS‐s‐C60 hybrid. Surface bonding of C60 molecules not only improves significantly the ambient stability of BPNSs, but also boosts dramatically the visible light and near‐infrared (NIR) photocatalytic hydrogen evolution rates, reaching 1466 and 1039 μmol h−1 g−1 respectively, which are both the highest values among all reported BP‐based metal‐free photocatalysts. [ABSTRACT FROM AUTHOR]

Excitation of photoactive electron donor−acceptor (EDA) complexes to generate radical is a promising approach in radical chemistry. In this study, we introduce a new model of H‐bonding EDA complexes for the selective hydrothiolation and hydroxysulfenylation of carbonyl‐activated alkenes with diverse thiols under visible light conditions. The reliability of this H‐bonding EDA complex model has been confirmed by meticulous experimental and theoretical calculations. Mechanistic investigations have revealed the significant influence of the solvent in determining whether the excitation of photoactive H‐bonding EDA complex leads to charge transfer (CT) or energy‐charge transfer (En‐CT), thereby controlling Markovnikov and anti‐Markovnikov selectivity. Notably, the Quantum Theory of Atoms in Molecules (QTAIM) analysis clearly shows that the excited state of the C=O−H−S EDA complex involves closed‐shell partially covalent interactions. [ABSTRACT FROM AUTHOR]

The valorization of native lignin to functionalized aromatic compounds under visible light is appealing yet challenging. In this communication, colloidal mercaptoalkanoic acid capped ultrathin ZnIn2S4 (ZIS) microbelts was successfully fabricated, which was used as a superior catalyst for depolymerization of native lignin in birch woodmeal under visible light, with an optimum yield of 28.8 wt % to functionalized aromatic monomers achieved in 8 h. The capped mercaptoalkanoic acid not only enables a solvent modulated reversible interchange of ZIS between the colloidal state for efficient reaction and the aggregated state for facile separation, but also serves as a precursor for light initiated generation of reactive thiyl radical for highly selective cleavage of β‐O‐4 bond in native lignin. This work provides a green and efficient strategy for the depolymerization of native lignin to functionalized aromatic monomers under mild conditions, which involves a new mechanism for the cleavage of β‐O‐4 bonds in native lignin. The capability of cleavage of β‐O‐4 bonds in native lignin by photogenerated thiyl radicals also demonstrates the great potential of using photogenerated thiyl radicals in organics transformations. [ABSTRACT FROM AUTHOR]

The fabrication of materials that can switch between circularly polarized luminescence (CPL) signals is both essential and challenging. Here, two new halogen‐bonded fluorescent molecular photoswitches, namely, HB‐switch 1 and HB‐switch 2, containing α‐cyano‐substituted diarylethene compounds with different end groups were developed. Upon exposure to specific UV or visible light wavelengths, they exhibited controllable and reversible Z/E photoisomerization. When these switches were integrated into blue‐phase liquid crystals (BPLCs), the temperature range of BP significantly expanded. Notably, the BP system incorporating HB‐switch 1 exclusively achieved reversible polarization inversion of CPL signals under irradiation with specific UV/Visible light and during cooling/heating. The photo/thermal dual‐response behavior of the CPL signals can be attributed to the phase transition from a high‐symmetry 3D BP Icubic lattice to a low‐symmetry 1D helical superstructure induced by the Z/E photoisomerization of HB‐switch 1 and temperature changes. This study underscores the significance of employing halogen‐bond assembly strategies to design materials with switchable CPL signals, opening new possibilities for CPL‐active systems. [ABSTRACT FROM AUTHOR]

Radical ipso‐substitution offers an alternative to organometallic approaches for biaryl synthesis, but usually requires stoichiometric reagents such as tributyltin hydride. Here, we demonstrate that visible light photoredox catalysis can be used for ipso‐biaryl synthesis, via a halogen‐atom transfer (XAT) regime. Using amide substrates that promote ipso‐ over unwanted ortho‐addition, we demonstrate smooth biaryl formation with no constraint on the electronic character of the migrating arene ring. The photoreaction can be combined in one operation to achieve a formal arylation of the inert aniline C−N bond. [ABSTRACT FROM AUTHOR]

In this work, six benzothioxanthene‐based oxime esters were employed as photoinitiators for photopolymerization under visible light (LED) and sunlight. Their abilities to behave as Type I photoinitiators by mean of a photocleavage mechanism of oxime esters but also in multicomponent photoinitiating systems with an iodonium salt (through an electron transfer mechanism) were both explored with the different structures. Due to their broad absorption spectra tailing up 600 nm, photoinitiating properties of the benzothioxanthene‐based oxime esters were systematically tested under excitation with low‐intensity LED light at wavelengths of 405 nm and 450 nm. Additionally, parallel to the polymerization tests done under artificial light, the different benzothioxanthene‐based oxime esters were also investigated as solar photoinitiators and displayed a high reactivity in France (Western Europe) even in winter conditions. For the best candidates i.e. the most reactive structures, direct laser write experiments were carried out, evidencing the interest of these structures. [ABSTRACT FROM AUTHOR]

In the presence of 1 mol % of a chiral iron porphyrin catalyst, various 3‐arylmethyl‐substituted 2‐quinolones and 2‐pyridones underwent an enantioselective amination reaction (20 examples; 93–99 % ee). The substrates were used as the limiting reagents, and fluorinated aryl azides (1.5 equivalents) served as nitrene precursors. The reaction is triggered by visible light which allows a facile dediazotation at ambient temperature. The selectivity of the reaction is governed by a two‐point hydrogen bond interaction between the ligand of the iron catalyst and the substrate. Hydrogen bonding directs the amination to a specific hydrogen atom within the substrate that is displaced by the nitrogen substituent either in a concerted fashion or by a rebound mechanism. [ABSTRACT FROM AUTHOR]

Recently, the introduction of fluorosulfonyl (−SO2F) groups have attracted considerable research interests, as this moiety could often afford enhanced activities and new functions in the context of chemical biology and drug discovery. Herein, we report the design and synthesis of 1‐fluorosulfamoyl‐pyridinium (FSAP) salts, which could serve as an effective photoredox‐active precursor to fluorosulfamoyl radicals and enable the direct radical C−H fluorosulfonamidation of a variety of (hetero)arenes. This method features mild conditions, visible light, broad substrate scope, good group tolerance, etc. and a metal‐free protocol is also viable by using organic photocatalysts. Further, FSAP can also be applied to the radical functionalization of alkenes via 1,2‐difunctionalization, radical distal migration, tandem radical‐polar crossover reactions, etc. In addition, a formal C−H methylamination of (hetero)arenes by combining this radical C−H fluorosulfonamidation with subsequent hydrolysis as well as product derivatization are also demonstrated. [ABSTRACT FROM AUTHOR]

Chemically fueled chemical reaction networks (CRNs) are essential in controlling dissipative self‐assembly. A key challenge in the field is to store chemical fuel‐precursors or "pre‐fuels" in the system that are converted into activating or deactivating fuels in a catalytically controlled CRN. In addition, real‐time control over catalysis in a CRN by light is highly desirable, but so far not yet achieved. Here we show a catalytically driven CRN that is photoinitiated with 450 nm light, producing activated monomers that go on to perform transient self‐assembly. Monomer activation proceeds via photoredox catalysis, converting the monomer alcohol groups into the corresponding aldehydes that self‐assemble into large supramolecular fibers. Monomer deactivation is achieved by organometallic catalysis that relies on pre‐fuel hydrolysis to release formate (i.e. the deactivating fuel). Additionally, irradiation with 305 nm light accelerates the release of formate by photo‐uncaging the pre‐fuel, leading to a factor of ca. 2 faster deactivation of the monomer. Overall, we show transient self‐assembly upon visible light photoactivation, and tunable life‐times by ultraviolet light. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 production from water via oxygen reduction reaction (ORR). The design of COFs for efficient H2O2 production indubitably hinges on an in‐depth understanding of their ORR mechanisms. In this work, taking an imine‐linked COF as an example, we demonstrate that protonation of the functional units such as imine, amine, and triazine, is a highly efficient strategy to upgrade the activity levels for H2O2 synthesis. The protonation not only extends the light absorption of the COF but also provides proton sources that directly participate in H2O2 generation. Notably, the protonation simplifies the reaction pathways of ORR to H2O2, i.e. from an indirect superoxide radical (O2•- ${{O}_{2}^{\bullet -}}$) mediated route to a direct one‐step two‐electron route. Theoretical calculations confirm that the protonation favors H2O2 synthesis due to easy access of protons near the reaction sites that removes the energy barrier for generating *OOH intermediate. These findings not only extend the mechanistic insight into H2O2 photosynthesis but also provide a rational guideline for the design and upgradation of efficient COFs. [ABSTRACT FROM AUTHOR]

Radical‐involved multicomponent difunctionalization of 1,3‐dienes has recently emerged as a promising strategy for rapid synthesis of valuable allylic compounds in one‐pot operation. However, the expansion of radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper‐catalyzed highly enantioselective three‐component radical 1,2‐azidooxygenation of 1,3‐dienes with readily available azidobenziodazolone reagent and carboxylic acids. This mild protocol exhibits a broad substrate scope, high functional group tolerance, and exceptional control over chemo‐, regio‐ and enantioselectivity, providing practical access to diverse valuable azidated chiral allylic esters. Mechanistic studies imply that the chiral copper complex is implicated as a bifunctional catalyst in both the photoredox catalyzed azidyl radical generation and enantioselective radical C−O cross‐coupling. [ABSTRACT FROM AUTHOR]

Top‐down control of small motion is possible through top‐down controlled molecular motors in replacement of larger actuators like MEMS or NEMS (micro‐ or nano‐electromechanical systems) in the current precision technology. Improving top‐down control of molecular motors to every single step is desirable for this purpose, and also for synchronization of motor actions for amplified effects. Here we report a designed single‐stranded DNA molecular motor powered by alternated ultraviolet and visible light for processive track‐walking, with the two light colours each locking the motor in a full directional step to allow saturated driving but no overstepping. This novel nano‐optomechanical driving mechanism pushes the top‐down control of molecular motors down to every single step, thus providing a key technical capability to advance the molecular motor‐based precision technology and also motor synchronization for amplified effects. [ABSTRACT FROM AUTHOR]

We report an iron‐catalyzed decarboxylative C(sp3)−O bond‐forming reaction under mild, base‐free conditions with visible light irradiation. The transformation uses readily available and structurally diverse carboxylic acids, iron photocatalyst, and 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) derivatives as oxygenation reagents. The process exhibits a broad scope in acids possessing a wide range of stereoelectronic properties and functional groups. The developed reaction was applied to late‐stage oxygenation of a series of bio‐active molecules. The reaction leverages the ability of iron complexes to generate carbon‐centered radicals directly from carboxylic acids by photoinduced carboxylate‐to‐iron charge transfer. Kinetic, electrochemical, EPR, UV/Vis, HRMS, and DFT studies revealed that TEMPO has a triple role in the reaction: as an oxygenation reagent, an oxidant to turn over the Fe‐catalyst, and an internal base for the carboxylic acid deprotonation. The obtained TEMPO adducts represent versatile synthetic intermediates that were further engaged in C−C and C‐heteroatom bond‐forming reactions using commercial organo‐photocatalysts and nucleophilic reagents. [ABSTRACT FROM AUTHOR]

Three‐dimensional covalent organic frameworks (3D COFs), recognized for their tailorable structures and accessible active sites, offer a promising platform for developing advanced photocatalysts. However, the difficulty in the synthesis and functionalization of 3D COFs hinders their further development. In this study, we present a series of 3D‐bcu‐COFs with 8 connected porphyrin units linked by linear linkers through imine bonds as a versatile platform for photocatalyst design. The photoresponse of 3D‐bcu‐COFs was initially modulated by functionalizing linear linkers with benzo‐thiadiazole or benzo‐selenadiazole groups. Furthermore, taking advantage of the well‐exposed porphyrin and imine sites in 3D‐bcu‐COFs, their photocatalytic activity was optimized by stepwise protonation of imine bonds and porphyrin centers. The dual protonated COF with benzo‐selenadiazole groups exhibited enhanced charge separation, leading to an increased photocatalytic H2O2 production under visible light. This enhancement demonstrates the combined benefits of linker functionalization and stepwise protonation on photocatalytic efficiency. [ABSTRACT FROM AUTHOR]

Oxygen vacancies (OV) in nonmetallic plasmonic photocatalysts can decrease the energy barrier for CO2 reduction, boosting C1 intermediate production for potential C2 formation. However, their susceptibility to oxidation weakens C1 intermediate adsorption. Herein we proposed a "photoelectron injection" strategy to safeguard OV in W18O49 by creating a W18O49/ZIS (W/Z) plasmonic photocatalyst. Moreover, photoelectrons contribute to the local multi‐electron environment of W18O49, enhancing the intrinsic excitation of its hot electrons with extended lifetimes, as confirmed by in situ XPS and femtosecond transient absorption analysis. Density functional theory calculations revealed that W/Z with OV enhances CO2 adsorption, activating *CO production, while reducing the energy barrier for *COH production (0.054 eV) and subsequent *CO−*COH coupling (0.574 eV). Successive hydrogenation revealed that the free energy for *CH2CH2 hydrogenation (0.108 eV) was lower than that for *CH2CH2 desorption for C2H4 production (0.277 eV), favouring C2H6 production. Consequently, W/Z achieves an efficient C2H6 activity of 653.6 μmol g−1 h−1 under visible light, with an exceptionally high selectivity of 90.6 %. This work offers a new strategy for the rational design of plasmonic photocatalysts with high selectivity for C2+ products. [ABSTRACT FROM AUTHOR]

The chemistry of light dipnictenes has been widely investigated in the last century with remarkable achievements especially for azobenzene derivatives. In contrast, distibenes and dibismuthenes are relatively rare and show very limited reactivity. Herein, we have designed a protocol using visible light to enhance the reactivity of heavy dipnictenes. Exploiting the distinctive π–π* transition, we have been able to isolate unique examples of dipnictene‐cobalt complexes. The reactivity of the distibene complex was further exploited using red light in the presence of a diazoolefin to access an unusual four‐membered bicyclo[1.1.0]butane analog, containing only a single carbon atom. These findings set the bases to a conceptually new strategy in heavy element double bonds chemistry where visible light is at the front seat of bond activation. [ABSTRACT FROM AUTHOR]

Despite the pivotal role of molecular oxygen (O2) activation in artificial photosynthesis, the activation efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)‐based imine‐linked covalent organic frameworks (COFs) with tailored donor‐acceptor (D–A) structures, TTF‐PDI‐COF and TTF‐TFPP‐COF, to promote O2 activation. Because of enhanced electron push‐pull interactions that facilitated charge separation and transfer behavior, TTF‐PDI‐COF exhibited superior photocatalytic activity in electron‐induced O2 activation reactions over TTF‐TFPP‐COF under visible light irradiation, including the photosynthesis of (E)‐3‐amino‐2‐thiocyano‐α,β‐unsaturated compounds and H2O2. These findings highlight the significant potential of the rational design of COFs with D–A configurations as suitable candidates for advanced photocatalytic applications. [ABSTRACT FROM AUTHOR]

The construction of C(sp3)−N bonds via direct N‐centered radical addition with olefins under benign conditions is a desirable but challenging strategy. Herein, we describe an organo‐photocatalytic approach to achieve anti‐Markovnikov alkene hydroamidation with sulfonyl azides in a highly efficient manner under transition‐metal‐free and mild conditions. A broad range of substrates, including both activated and unactivated alkenes, are suitable for this protocol, providing a convenient and practical method to construct sulfonylamide derivatives. A synergistic experimental and computational mechanistic study suggests that the additive, Hantzsch ester (HE), might undergo a triplet‐triplet energy transfer manner to achieve photosensitization by the organo‐photocatalyst under visible light irradiation. Next, the resulted triplet excited state 3HE* could lead to a homolytic cleavage of C4−H bond, which triggers a straightforward H‐atom transfer (HAT) style in converting sulfonyl azide to the corresponding key amidyl radical. Subsequently, the addition of the amidyl radical to alkene followed by HAT from p‐toluenethiol could proceed to afford the desired anti‐Markovnikov hydroamidation product. It is worth noting that mechanistic pathway bifurcation could be possible for this reaction. A feasible radical chain propagation mechanistic pathway is also proposed to rationalize the high efficiency of this reaction. [ABSTRACT FROM AUTHOR]

The modification of polymer surfaces using laser light is important for many applications in the nano‐, bio‐ and chemical sciences. Such capabilities have supported advances in biomedical devices, electronics, information storage, microfluidics, and other applications. In most cases, these modifications require high power lasers that are expensive and require specialized equipment and facilities to minimize risk of hazardous radiation. Additionally, polymer systems that can be easily modified by lasers are often complex and costly to prepare. In this report, these challenges are addressed with the discovery of low‐cost sulfur copolymers that can be rapidly modified with lasers emitting low‐power infrared and visible light. The featured copolymers are made from elemental sulfur and either cyclopentadiene or dicyclopentadiene. Using a suite of lasers with discreet wavelengths (532, 638 and 786 nm) and powers, a variety of surface modifications could be made on the polymers such as controlled swelling or etching via ablation. The facile synthesis and laser modification of these polymer systems were exploited in applications such as direct laser lithography and erasable information storage. [ABSTRACT FROM AUTHOR]

Engineering advantageous defects to construct well‐defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe‐based metal‐organic framework (MOF) photocatalysts via a non‐thermal plasma‐assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH− and H2O). Specially, the optimized MIL‐100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7‐ and 7.7‐fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d‐orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high‐performance activation of catalytic molecules. [ABSTRACT FROM AUTHOR]

Nanozymes possess multi‐enzyme activities over the natural enzymes, which produce multi‐pathway synergistic effects for varies of biomedical applications. Unfortunately, their multi‐enzyme activities are in fighting, significantly reducing the synergistic effects. Dynamic regulation of their multi‐enzyme activities is the bottleneck for intelligent therapies. Herein, we construct a novel oxygen‐nitrogen functionalized carbon quantum dots (O/N‐CQDs) with peroxidase‐like (Reactive oxygen species (ROS) producer) activity. Interestingly, the peroxidase‐like activity can be reversibly converted to catalase‐like (ROS scavenger) activity under visible light irradiation. It is found that both the peroxidase/catalase‐like activity of O/N‐CQDs can be precisely manipulated by the light intensity. The mechanism of switchable enzyme activities is attributed to the polarization of quinoid nitrogen in polyaniline (PANI) precursor retained on O/N‐CQDs under visible light, which consumes the ROS to produce O2 and H2O. As a proof‐of‐concept demonstration, we are able to non‐intrusively up and down regulate the ROS level in cells successfully by simply switching off and on the light respectively, potentially facilitating the precise medicine based on the development of the disease. Indeed, the photo‐switchable peroxidase/catalase‐like activity of O/N‐CQDs opens a non‐invasive strategy for better manipulations of the multi‐activity of nanozymes, promising their wider and more intelligent biomedical applications. [ABSTRACT FROM AUTHOR]

The exfoliation of bulk C3N4 (BCN) into ultrathin layered structure is an effective strategy to boost photocatalytic efficiency by exposing interior active sites and accelerating charge separation and transportation. Herein, we report a novel nitrate anion intercalation‐decomposition (NID) strategy that is effective in peeling off BCN into few‐layer C3N4 (fl‐CN) with tailored thickness down to bi‐layer. This strategy only involves hydrothermal treatment of BCN in diluted HNO3 aqueous solution, followed by pyrolysis at various temperatures. The decomposition of the nitrate anions not only exfoliates BCN and changes the band structure, but also incorporates oxygen species onto fl‐CN, which is conducive to O2 adsorption and hence relevant chemical processes. In photocatalytic O2 reduction under visible light irradiation, the H2O2 production rate over the optimal fl‐CN‐530 catalyst is 952 μmol g−1 h−1, which is 8.8 times that over BCN. More importantly, under full arc irradiation and in the absence of hole scavenger, CH4 can be photocatalytically oxidized by on‐site formed H2O2 and active oxygen species to generate value‐added C1 oxygenates with high selectivity of 99.2 % and record‐high production rate of 1893 μmol g−1 h−1 among the metal‐free C3N4‐based photocatalysts. [ABSTRACT FROM AUTHOR]

The development of highly thermally conductive composites that combine visible light/infrared camouflage and information encryption has been endowed with great significance in facilitating the application of 5G communication technology in military fields. This work uses aramid nanofibers (ANF) as the matrix, hetero‐structured silver nanowires@boron nitride nanosheets (AgNWs@BNNS) prepared by in situ growth as fillers, which are combined to fabricate sandwich structured thermally conductive and electrically insulating (BNNS/ANF)‐(AgNWs@BNNS)‐(BNNS/ANF) (denoted as BAB) composite films by "filtration self‐assembly, air spraying, and hot‐pressing" method. When the mass ratio of AgNWs@BNNS to BNNS is 1 : 1 and the total mass fraction is 50 wt %, BAB composite film has the maximum in‐plane thermal conductivity coefficient (λ∥ of 10.36 W/(m ⋅ K)), excellent electrical insulation (breakdown strength and volume resistivity of 41.5 kV/mm and 1.21×1015 Ω ⋅ cm, respectively) and mechanical properties (tensile strength of 170.9 MPa). 50 wt % BAB composite film could efficiently reduce the equilibrium temperature of the central processing unit (CPU) working at full power, resulting in 7.0 °C lower than that of the CPU solely integrated with ANF directly. In addition, BAB composite film boasts adaptive visible light/infrared dual camouflage properties on cement roads and jungle environments, as well as the function of fast encryption of QR code information within 24 seconds. [ABSTRACT FROM AUTHOR]

Improving the photoswitching rate and robustness of photochromic molecules in bulk solids is paramount for practical applications but remains an on‐going challenge. Here, we introduce an octupolar design paradigm to develop a new family of visible light organic photoswitches, namely multi‐branched octupolar Stenhouse Adducts (MOPSAs) featuring a C3‐symmetrical A3‐(D‐core) architecture with a dipolar donor–acceptor (D–A) photochrome in each branch. Our design couples multi‐dimensional geometric and electronic effects of MOPSAs to enable robust ultrafast reversible photoswitching in bulk polymers. Specifically, the optimal MOPSA (4 wt %) in commercial polyurethane films accomplishes nearly 100 % discoloration in 6 s under visible light with ∼ 100 % thermal‐recovery in 17.4 s at 60 °C, while the acquired kinetics constants are 3∼7 times that of dipolar DASA counterpart and 1∼2 orders of magnitude higher than those of reported DASAs in polymers. Importantly, the MOPSA‐doped polymer films sustain 500 discoloration/recovery cycles with slow degradation, superior to the existing DASAs in polymers (≤30 cycles). We discover that multi‐dipolar coupling in MOPSA enables enhanced polarization and electron delocalization, promoting the rate‐determining thermal cyclization, while the branched and non‐planar geometry of MOPSA induces large free volume to facilitate the isomerization. This design can be extended to develop spiropyran or azobenzene‐based ultrafast photochromic films. The superior photoswitching performance of MOPSAs together with their high‐yield and scalable synthesis and facile film processing inspires us to explore their versatile uses as smart inks or labels for time‐temperature indicators, optical logic encryption and multi‐levelled data encryption. [ABSTRACT FROM AUTHOR]

Efficient solar‐driven syngas production (CO+H2 mixture) from CO2 and H2O with a suitable photocatalyst and fundamental understanding of the reaction mechanism are the desired approach towards the carbon recycling process. Herein, we report the design and development of an unique COF‐topological quantum material nano‐heterostructure, COF@TI with a newly synthesized donor‐acceptor based COF and two dimensional (2D) nanosheets of strong topological insulator (TI), PbBi2Te4. The intrinsic robust metallic surfaces of the TI act as electron reservoir, minimising the fast electron‐hole recombination process, and the presence of 6s2 lone pairs in Pb2+ and Bi3+ in the TI helps for efficient CO2 binding, which are responsible for boosting overall catalytic activity. In variable ratio of acetonitrile‐water (MeCN : H2O) solvent mixture COF@TI produces syngas with different ratios of CO and H2. COF@TI nano‐heterostructure enables to produce higher amount of syngas with more controllable ratios of CO and H2 compared to pristine COF. The electron transfer route from COF to TI was realized from Kelvin probe force microscopy (KPFM) analysis, charge density difference calculation, excited state lifetime and photoelectrochemical measurements. Finally, a probable mechanistic pathway has been established after identifying the catalytic sites and reaction intermediates by in situ DRIFTS study and DFT calculation. [ABSTRACT FROM AUTHOR]

A sequential process via photoredox catalysis and Lewis acid mediation for C−F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation. [ABSTRACT FROM AUTHOR]

Copper nitrenoids are key intermediates in copper‐catalyzed direct C−H amination reactions. Further development of this important reaction relies on knowing the properties and reactivity of the nitrenoid intermediates. This work utilizes antenna ligands to form copper nitrenoid complexes and monitor the consecutive C−H amination reactions under well‐defined single‐molecule conditions in the gas phase. The [Cu(Lphoto)(Lazide)]+ precursors (Lphoto is a bidentate antenna ligand, and Lazide is an organic azide) were stored in an ion trap at 3.5 K and irradiated by visible light, which resulted in denitrogenation of the complex. Further irradiation of the copper nitrenoid led to the consecutive C−H amination of the antenna ligand. The nitrenoid complexes, as well as the products of the C−H amination, were characterized by helium tagging IRPD spectroscopy, and the mechanism was described by DFT calculations. This research demonstrates that the antenna ligands can be used to promote the denitrogenation of metal azides in the gas phase and also channel the internal energy to promote further reactivity, which opens a new way to study the reactivity of highly reactive species under well‐defined conditions. [ABSTRACT FROM AUTHOR]

2‐Acetonaphthones, which bear an alkenyl group tethered to its C1 carbon atom via an oxygen atom, were found to undergo an enantioselective intramolecular ortho photocycloaddition reaction. A chiral oxazaborolidine Lewis acid leads to a bathochromic absorption shift of the substrate and enables an efficient enantioface differentiation. Visible light irradiation (λ=450 nm) triggers the reaction which is tolerant of various groups at almost any position except carbon atom C8 (16 examples, 53–99 % yield, 80–97 % ee). Consecutive reactions were explored including a sensitized rearrangement to tetrahydrobiphenylenes, which occurred with full retention of configuration. Evidence was collected that the catalytic photocycloaddition occurs via triplet intermediates, and the binding mode of the acetonaphthone to the chiral Lewis acid was elucidated by DFT calculations. [ABSTRACT FROM AUTHOR]

Photocatalytic selective oxidation under visible light presents a promising approach for the sustainable transformation of biomass‐derived wastes. However, achieving both high conversion and excellent selectivity poses a significant challenge. In this study, two valuable trioses, glyceraldehyde and dihydroxyacetone, are produced from glycerol over Cuδ+‐decorated WO3 photocatalyst in the presence of H2O2. The photocatalyst exhibits a remarkable five‐fold increase in the conversion rate (3.81 mmol ⋅ g−1 ⋅ h−1) while maintaining a high selectivity towards two trioses (46.4 % to glyceraldehyde and 32.9 % to dihydroxyacetone). Through a comprehensive analysis involving X‐ray photoelectron spectroscopy measurements with and without light irradiation, electron spin resonance spectroscopy, and isotopic analysis, the critical role of Cu+ species has been explored as efficient hole acceptors. These species facilitate charge transfer, promoting glycerol oxidation by photoholes, followed by coupling with OH‐, which are subsequently dehydrated to yield the desired glyceraldehyde and dihydroxyacetone. [ABSTRACT FROM AUTHOR]

Modifying redox potential of substrates and intermediates to balance pairs of redox steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration of iridium photosensitizer and imine substrate within one packet of a metal‐organic capsule to shift the redox potentials of substrate, herein, we reported a multiphoton enzymatic strategy for the generation of heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated a pre‐equilibrium substrate‐involving clathrate that cathodic shifts the oxidation potential of the substrate‐dye‐host ternary complex and configuration inversion of substrate via spatial constraints in the confined space. The new two photon excitation strategy enabled the precise control of the multistep electron transfer between each pair (photosensitizer, substrate and the capsule), endowing the catalytic system proceeding smoothly with an enzymatic fashion. Three kinds of 2‐subsituted (−OH, −NH2, and −SH) imines and N‐aryl enamines all give the corresponding cyclization products efficiently under visible light irradiation, demonstrating the promising of the microenvironment driven thermodynamic activation in the host‐dye‐substrate ternary for synergistic combination of multistep photocatalytic transformations. [ABSTRACT FROM AUTHOR]

Plasmonic catalysis has emerged as a promising approach to solar‐chemical energy conversion. Notably, hot carriers play a decisive role in plasmonic catalysis since only when their energy matches with the LUMO or HOMO energy of the reactant molecule, can the reaction be activated. However, the hot carrier energy depends on the intrinsic physicochemical properties of the plasmonic metal substrate and the interaction with incident light. Tuning the hot carrier energy is of great significance for plasmonic catalysis but remains challenging. Here, we demonstrate that the energy of hot electrons can be significantly elevated to an unprecedented level through the coordination of amines on Ag surface. The bonding of amines and Ag reduces the work function of nanoparticles, leading to the increase of hot electron energy by 0.4 eV. This enhancement of energy promotes the cleavage of C−X (X=Cl, F) bonds upon excitation by visible light. This study provides new insights for promoting plasmonic charge transfer and enhancing the photocatalytic performance of plasmon‐mediated systems. [ABSTRACT FROM AUTHOR]

Exploring unique single‐atom sites capable of efficiently reducing O2 to H2O2 while being inert to H2O2 decomposition under light conditions is significant for H2O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single‐Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single‐Zn sites on CN, forming asymmetric Zn−N3O moiety on CN (denoted as CN/Zn−OAc), in contrast to the obtained Zn−N4 sites when sulfate (SO4) is adopted (CN/Zn−SO4). Both experimental and theoretical investigations demonstrate that the Zn−N3O moiety exhibits higher intrinsic activity for O2 reduction to H2O2 than the Zn−N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn−OAc catalyst exhibits significantly improved photocatalytic H2O2 production activity under visible light irradiation. [ABSTRACT FROM AUTHOR]

Diarylethene molecular photoswitches hold great fascination as optical information materials due to their unique bistability and exceptional reversible photoswitching properties. Conventional diarylethenes, however, rely on UV light for ring‐closure reactions, typically with modest yields. For practical application, diarylethenes driven by visible lights are preferred but achieving high ring‐closure reaction yield remains a significant challenge. Herein, we synthesized a novel all‐visible‐light‐driven photoswitch, TPAP−DTE, by facilely endcapping the dithienylethene (DTE) core with triphenylamine phenyl (TPAP) groups. Owing to the electron‐donating conjugation effect of TPAP, the open‐form TPAP−DTE responds strongly to short‐wavelength visible lights with considerable photocyclization quantum yields and molar absorption coefficient. Upon 405 nm visible‐light irradiation, TPAP−DTE achieves a ring‐closure reaction yield exceeding 96.3 % (confirmed by both nuclear magnetic resonance spectroscopy and high‐performance liquid chromatography). Its ring‐opening reaction yield is 100 % upon irradiation with long‐wavelength visible light. TPAP−DTE could be regarded as a bidirectional "quasi"‐quantitative conversion molecular switch. Furthermore, TPAP−DTE exhibits robust fatigue resistance over 100 full photoswitching cycles and great anti‐aging property under 85 °C and 85 % humidity for at least 1000 h. Consequently, its rewritable QR‐code, multilevel data storage, and anti‐counterfeiting/encryption applications are successfully demonstrated exclusively using visible lights, positioning TPAP−DTE as a highly promising medium for information recording. [ABSTRACT FROM AUTHOR]

Herein, we report the use of isonitriles as alkyl radical precursors in light‐mediated hydro‐ and deuterodeamination reactions. The reaction is scalable, shows broad functional group compatibility and potential to be used in late‐stage functionalization. Importantly, the method is general for Cα‐primary, Cα‐secondary and Cα‐tertiary alkyl isonitriles. For most examples, high yields were obtained through direct visible‐light irradiation of the isonitrile in the presence of a silyl radical precursor. Interestingly, in the presence of an organic photocatalyst (4CzIPN) a dramatic acceleration was observed. In‐depth mechanistic studies using UV/Vis absorption, steady‐state and time‐resolved photoluminescence, and transient absorption spectroscopy suggest that the excited state of 4CzIPN can engage in a single‐electron transfer with the isonitrile. [ABSTRACT FROM AUTHOR]

Organic materials exhibiting long‐lasting emission in the near infrared are expected to have applications in bio‐imaging and other areas. Although room temperature phosphorescence and thermally activated delayed fluorescence display long‐lived emission of approximately one minute, organic long‐persistent luminescence (OLPL) systems with a similar emission mechanism to inorganic persistent emitters can emit for several hours at room temperature. In particular OLPL with a hole‐diffusion mechanism can function even in the presence of oxygen. However, ionic materials lack long‐term stability in neutral organic host owing to aggregation and phase separation. In this study, we synthesized polymers with stable near‐infrared persistent luminescence at room temperature via the copolymerization of electron donors and acceptors. The copolymers exhibit long‐persistent luminescence (LPL) at temperatures below the glass transition temperature and can be excited by approximately the entire range of visible light. LPL properties and spectra can be controlled by the dopant. [ABSTRACT FROM AUTHOR]

Aryl‐maleimides undergo a novel [2+4]‐photodimerization instead of the expected [2+2]‐photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl‐maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non‐bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions. [ABSTRACT FROM AUTHOR]

Boronate rearrangements, such as the Matteson and Petasis reactions, are valuable metal‐free reactions for the transfer of the carbo group on boron to intramolecular electrophilic sites. However, only highly reactive electrophiles are suitable, and ketones are too inactive for those boronate rearrangements due to the high energy barriers. We disclose here the 1,3‐boronate rearrangement to ketones, for which a high energy barrier (44.9 kcal/mol) is prohibitory for thermal reactions in the ground state. The reaction is enabled by the key keto‐enol‐boronate bidentate complex formation in situ, which absorbs visible light to reach the excited state for the chemoselective 1,3‐boronate rearrangement to ketones. Experimental and computational investigations exclude free radical intermediates from organoboronates. The aryl, alkenyl, and alkyl boronic acids react with various 1,3‐diketones driven by visible light irradiation to construct structurally diverse β‐keto tertiary alcohols under metal‐free conditions. The reaction demonstrates substrate diversity with 58 examples, yields up to 98 %, and it is suitable for gram‐scale synthesis. [ABSTRACT FROM AUTHOR]

The development of stimuli‐responsive artificial H+/Cl− ion channels, capable of specifically disturbing the intracellular ion homeostasis of cancer cells, presents an intriguing opportunity for achieving high selectivity in cancer therapy. Herein, we describe a novel family of non‐covalently stapled self‐assembled artificial channels activatable by biocompatible visible light at 442 nm, which enables the co‐transport of H+/Cl− across the membrane with H+/Cl− transport selectivity of 6.0. Upon photoirradiation of the caged C4F‐L for 10 min, 90 % of ion transport efficiency can be restored, giving rise to a 10.5‐fold enhancement in cytotoxicity against human colorectal cancer cells (IC50=8.5 μM). The mechanism underlying cancer cell death mediated by the H+/Cl− channels involves the activation of the caspase 9 apoptosis pathway as well as the scarcely reported disruption of the autophagic processes. In the absence of photoirradiation, C4F‐L exhibits minimal toxicity towards normal intestine cells, even at a concentration of 200 μM. [ABSTRACT FROM AUTHOR]

N‐Trifluoromethylated organics may be applied in drug design, agrochemical synthesis, and materials science, among other areas. Yet, despite recent advances in the synthesis of aliphatic, cyclic and heterocyclic N‐trifluoromethyl compounds, no strategy based on trifluoromethyl nitrene has hitherto been explored. Here we describe the formation of triplet trifluoromethyl nitrene from azidotrifluoromethane, a stable and safe‐to‐use precursor, by visible light photocatalysis. The addition of CF3N to alkenes via biradical intermediates afforded previously unknown aziridines substituted with trifluoromethyl group on the nitrogen atom. The obtained aziridines were converted into either N‐trifluoromethylimidazolines, via formal [3+2] cycloaddition with nitriles, mediated by a Lewis acid, or into N‐trifluoromethylaldimines, via ring opening and aryl group migration mediated by a strong Brønsted acid. Our findings open new opportunities for the development of novel classes of N‐CF3 compounds with possible applications in the life sciences. [ABSTRACT FROM AUTHOR]

The development of ultra‐long room‐temperature phosphorescence (UL‐RTP) in processable amorphous organic materials is highly desirable for applications in flexible displays, anti‐counterfeiting, and bio‐imaging. However, achieving efficient UL‐RTP from amorphous materials remains a challenging task, especially with activation by visible light and a bright afterglow. Here we report a general and rational molecular‐design strategy to enable efficient visible‐light‐excited UL‐RTP by multi‐esterification of a rigid large‐plane phosphorescence core. Notably, multi‐esterification minimizes the aggregation‐induced quenching and accomplishes a ′four birds with one stone′ possibility in the generation and radiation process of UL‐RTP: i) shifting the excitation from ultraviolet light to blue‐light through enhancing the transition dipole moment of low‐lying singlet‐states, ii) facilitating the intersystem crossing process through the incorporation of lone‐pair electrons, iii) boosting the decay process of long‐lived triplet excitons resulting from a significantly increased transition dipole moment, and iv) reducing the intrinsic triplet nonradiative decay by substitution of high‐frequency vibrating hydrogen atoms. All these factors synergistically contribute to the most efficient and stable visible‐light‐stimulated UL‐RTP (lifetime up to 2.01 s and efficiency up to 35.4 % upon excitation at 450 nm) in flexible films using multi‐esterified coronene, which allows high‐tech applications in single‐component time‐delayed white light‐emitting diodes and information technology based on flashlight‐activated afterglow encryption. [ABSTRACT FROM AUTHOR]

Light‐driven multicolor supramolecular systems mainly rely on the doping of dyes or a photo‐reaction to produce unidirectional luminescence. Herein, we use visible light to drive the bidirectional reversible multicolor supramolecular shuttle from blue to green, white, yellow, up to orange by simple encapsulation of spiropyran‐modified cyanostilbene (BCNMC) by the macrocyclic cucurbit[8]uril (CB[8]) monomer. The resultant host–guest complex displayed enhanced fluorescence properties, i.e. the multicolor fluorescence shuttle changed from blue to orange in the dark within 2 hours and reverted to the original state upon visible light irradiation for 30 s. Benefiting from the sensitivity of the spiropyran moiety to light, it can spontaneously isomerize from the ring‐opened state to a ring‐closed isomer in aqueous solution, and this photo‐isomerization reaction is a reversible process under visible light irradiation, leading to the multicolor luminescence supramolecular shuttle as a result of intramolecular energy transfer. In addition, the light also drove the reversible conversion of the topological morphology of the host–guest complex from two‐dimensional nanoplatelets to nanospheres. Different from the widely reported molecular rotaxane "shuttle", the spiropyran supramolecular shuttle confined in the macrocyclic host CB[8] not only modulated a reversible topological morphology by light but also exhibited multicolor luminescence, which was successfully applied in programmed and rewritable information encryption. [ABSTRACT FROM AUTHOR]

Molecular photoswitching with red light is greatly desired to evade photodamage and achieve specific photoresponses. In virtually all reported cases however, only one switching direction uses red light while for the reverse switching, UV or visible light is needed. All‐red‐light photoswitching brings with it the clear advantage of pushing photoswitching to the limit of the low‐energy spectrum, but no viable system is available currently. Here we report on peri‐anthracenethioindigo (PAT) as molecular scaffold for highly efficient all‐red‐light photoswitching with an outstanding performance and property profile. The PAT photoswitch provides near‐infrared (NIR) absorption up to 850 nm, large negative photochromism with more than 140 nm maxima shifts and changes color from green to blue upon irradiation with two shades of red light. Thermal stability of the metastable Z isomer is high with a corresponding half‐life of days at 20 °C. Application in red‐light responsive polymers undergoing pronounced and reversible green to blue color changes demonstrate spatially resolved photoswitching. The PAT photoswitch thus offers unique responsiveness to very low energy light together with predictable and large geometrical changes within a rigid molecular scaffold. We expect a plethora of applications for PAT in the near future, e.g. in materials, molecular machines or biological context. [ABSTRACT FROM AUTHOR]