Chemistry - A European Journal

Biomacromolecules such as DNA, proteins, and lipids in nature are constructed by 'bottom‐up' assembly with diverse functions and structural ordered characteristics. Supramolecular assemblies have been employed to mimic the natural complexity by manipulating the subtle variations of functional groups. Nevertheless, the intricate design of the driving forces or sophisticated synthesis of molecular skeletons poses challenges in fabricating highly ordered assemblies. Natural phenolic molecules with anisotropic functional groups exhibit potential as versatile building blocks for a wide range of supramolecular crystalline materials with tailored assembly and controlled functionalities. The inherent and anisotropic phenolic groups engage in ordered assembly with various materials via directional covalent bonds (e.g., condensation and coordination) as well as multiple molecular interactions (e.g., hydrogen bonding and π–π interactions), leading to the formation of supramolecular crystalline materials with diverse functionalities. This Concept presents the assembly mechanisms of crystalline phenolic materials and their applications, showcasing the effective utilization of ordered assembly by natural phenolic building blocks.

Research into new antibiotics is becoming increasingly important as antibiotic resistance increases worldwide. The genus Streptomyces in particular is able to produce a wide range of antimicrobial products due to the large number of biosynthetic gene clusters (BGCs) in its genome. However, not all BGCs are expressed under laboratory conditions. In this work, deletion of the gene wblA, encoding a global regulator of natural product biosynthesis and morphogenesis in Streptomyces, led to the production of a novel natural product, olikomycin A, in Streptomyces ghanaensis ATCC 14672. Complete structure elucidation revealed that olikomycin A belongs to a class of calcium-dependent antibiotics known as non-ribosomal peptide synthetase (NRPS)-encoded acidic lipopeptides. These compounds exhibit remarkable antimicrobial activity in the presence of calcium. Insights into olikomycin A biosynthesis were provided by whole genome sequencing and gene inactivation studies, while bioactivity assays showed strong inhibition of the growth of multidrug-resistant Gram-positive pathogens via disrupting cell membrane integrity. Olikomycin A shows an antibiotic profile similar to that of daptomycin, which is already in clinical use.

The dimeric calcium and magnesium hydrides, [(BDI)AeH]2 [BDI = HC{(Me)CNDipp}2, Dipp = 2,6‐i‐Pr­2C6H3;­ Ae = Mg or Ca] do not react with Ph3GeH in non‐coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae‐germanide complexes, [(BDI)Ae{GePh3}(THF)], both of which have been structurally characterized. Although this process is facile when Ae = Ca, the analogous magnesium‐based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl‐C‐terminated n‐butoxide, [(BDI)|Mg{μ2‐O(CH2)4GePh3}]. Reactions of [(BDI)Ca{GePh3}(THF)] with N,N'‐di‐isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i‐PrN)2CGePh3}(THF)] and [(BDI)Ca{OC(GePh3)Ph2}(THF)], demonstrating its potential as a well‐defined and soluble source of the [Ph3Ge]− anion in nucleophilic addition reactions.

Oxygen plays a central role in biomolecular structures and functions, with 17O NMR emerging as a powerful tool for elucidating biomolecular properties. However, the low natural abundance of the NMR‐active isotope, 17O (0.0373%), presents a significant hurdle to its widespread application. Here, we introduce a rapid and cost‐effective approach for amino acid‐specific 17O‐labeling of recombinant proteins. Using a common bacterial expression system and with a 30‐minute rapid synthesis protocol of 17O‐labeled amino acids via mechanochemical saponification, we have generated Leu‐ and Phe‐specific 17O‐labeled recombinant proteins derived from diverse organisms, including CrgA and FtsQ from Mycobacterium tuberculosis and E protein from SARS‐CoV‐2 virus, demonstrating the applicability of our technique for amino acids known to be isotopically labeled without scrambling. We have acquired magic‐angle‐spinning 17O NMR of these proteins to confirm the successful 17O labeling and illustrate the sensitivity of 17O NMR to the protein’s local structural environments. Our work significantly broadens the accessibility of 17O‐NMR, empowering researchers to delve deeper into protein biophysics and biochemistry. This approach opens new avenues for understanding cellular processes at the molecular level by providing an effective tool for investigating oxygen‐related interactions and chemistry within biomolecules.

Several gallylenes [LPhGaM(THF)n] stabilized by an α‐diimine ligand (LPh=[(2,6‐iPr2C6H3)NC(Ph)]2²⁻; M=Li, n=3, 3‐Li; M=Na, n=4, 3‐Na; M=K, n=1, 3‐K) were prepared, which display diverse reactivities toward carbon dioxide and its sulfurized analogues. The reaction of 3 with CO2 yielded a trimeric carbonate complex [{LPhGa(CO3)2}3{μ‐K9(THF)6}] (4) and a dinuclear oxo‐carbonate complex [K2(THF)6][LPhGa(μ‐CO3)(μ‐O)GaLPh] (5) in one pot through reductive disproportionation of CO2. For CS2, two ethenetetrathiolate gallium complexes, [M2(Solv)4][LPhGa(μ‐C2S4)GaLPh] (M=Na, Solv=THF, 6; M=K, Solv=DME, 7), were obtained via reductive coupling of CS2. In the case of COS, disproportionation gave a disulfide‐bridged complex [K2(THF)6] [LPhGa(μ‐S)2GaLPh] (8) at room temperature, but a dithiocarbonate [Na2(THF)5][LPhGa(S2CO)]2 (9) at low temperature, the latter being the first example of dithiocarbonates of p‐block elements.

Since aggregation‐induced electrochemiluminescence (AIECL) luminophore overcomes the restriction of aggregation‐caused quenching in solid luminescent materials, AIECL luminophore has become a promising material in the field of electrochemiluminescence (ECL) engineering. However, the lack of ECL emitters with high AIECL performance limits its wide application. Herein, imine‐linked covalent organic frameworks (COFs) with C4 symmetrical tetraphenyl ethylene and C2 symmetrical five‐membered heteroaromatic monomers are designed as ECL emitter in aqueous media. Significantly, the ECL intensity of COFs with terthienyl units (TTA‐TAPE) is 206 times that of COFs with furan units in the presence of tri‐n‐propylamine (TPrA), which is the result of enhancing ECL signals by increasing the thiophene units and π‐π conjugation of COFs. Furthermore, the ECL mechanism of these COFs is vested in the bandgap model. Thus, the study provides a strategy for designing highly efficient ECL‐active COFs emitters with excellent AIECL efficiency.

Phosphenium ions are highly reactive species with the formula of RR`P+. Although phosphenium ions were proposed as the invaluable intermediates of various important chemical processes, the methods to generate and characterize them were very limited. In this study, a novel photoprecursor to give rise to the arylphosphenium ions, 1‐(naphthalen‐2‐yl)phosphirane, was synthesized and investigated by femtosecond to nanosecond transient absorption spectroscopies, photoproduct analysis, and density functional theory calculations. Subsequent to photoexcitation, the S1 state of the photoprecursor of interest is populated from the higher excited states, accompanied by the generation of an unexpected 2H‐phosphirene, 7bH‐naphtho[1,2‐b]phosphirene. After that, the resulted 2H‐phosphirene is protonated by H2O in the solvent to generate the naphthalen‐2‐yl(hydryl)phosphenium ion, which can be attacked by H2O and oxidized by O2 to give naphthalen‐2‐ylphosphinic acid as the major final product. The presence of these transient species is confirmed by density functional theory calculation and control experiments with different solvents. This study provides an understanding of the reactivity of arylphosphenium ions as well as 2H‐phosphirenes, and provides a novel method to generate and characterize these reactive species, which may help to further reveal their reactivity and explore their chemistry and use in a range of applications.

Obtaining a robust electrode composed of Sn‐based metal oxides and carbonaceous matrix through nanoscale structure engineering is essential for effectively improving Li‐ion batteries' electrochemical performance and stability. Herein, we report a bimetallic MoO2‐xSnO2/Sn nanoparticles uniformly anchored on N, S co‐doped graphene nanosheets (MoO2‐xSnO2/Sn@NSG) as an anode electrode for Li‐ion battery via a one‐step hydrothermal and thermal treatment approach. In the MoO2‐xSnO2/Sn nanocomposite, the generated Sn‐O‐Mo bond can modulate the electronic and composition structures to improve the intrinsic conductivity of SnO2 and reinforce the structural stability during cycles. Moreover, featuring excellent electronic conductivity via coupling of MoO2‐xSnO2/Sn and hierarchical NBG matrix, the MoO2‐xSnO2/Sn@NSG electrode possesses ultrafast electrochemical kinetics and superior long‐term cycling stability and rate capability. Additionally, the hierarchical MoO2‐2SnO2/Sn@NSG can suppress the aggregation and accommodate the volume variations of active substances, thereby providing more lithium storage sites. Consequently, the optimized MoO2‐2SnO2/Sn@NSG anode exhibits a high reversible capacity of 904 mA h g‐1 at 0.2 A g‐1 and excellent cycling performance with the reversible capacity of 456 mAh g‐1 at 1 A g‐1 over 600 cycles. The universal synthesis technology of bimetallic oxide anodes for advanced LIBs may provide vital guidance in designing high‐performance energy‐storage materials.

Dipolar fluorescent molecular rotors (FMRs) are environmentally‐sensitive fluorophores that can be used in bioimaging applications to sense local viscosity and polarity. Their sensitivity to viscosity can also be used for the fluorogenic labeling of biomolecules such as DNA or proteins. In particular, we have previously used FMRs to develop a series of tunable fluorogens targeting the self‐labeling protein tag Halotag for wash‐free protein imaging in live cells. Despite these very useful properties, FMRs typically display moderate molar absorption coefficients that limits their overall fluorescence brightness. Herein, we synthesized a series of three model hemicyanines based on a styrylindolenium scaffold and performed a detailed study of their photophysical properties in solvents with various polarity and viscosity. We show that with a strong julolidine electron‐donating group it is possible to combine intense cyanine‐like absorption with the high sensitivity to viscosity of FMRs. We use this property to develop a lysosomal pH sensor and two bright cell‐impermeant fluorogens targeting HaloTag for imaging membrane proteins. We believe that this bright fluorogenic scaffold based on a simple chemical structure can be used in the future to build up a variety of probes and sensors with efficient photophysical properties.

Ni2+ activated phosphor has attracted wide attention because it can be radiated in near‐infrared (NIR) II‐III region; however, the low external quantum yield (EQY) hinders its further application (most are below 8%). In this work, distortion of crystallographic site strategy is proposed to enhance EQY. LaTiTaO6: 0.004Ni2+ exhibits an NIR emitting spectrum centered at 1450 nm with an EQY of ~ 9.00%, which has been the highest EQY of reported Ni2+ single‐doped phosphor. Distortion degrees of the octahedral geometry in LaTiTaO6 and LaTiTaO6: 0.004Ni2+ changing from 0.038 to 0.047 result in the absorption efficiency of 38.6% due to the breaking of parity forbidden of the d‐d transition, further improving the EQY. Besides, LaTiTaO6: 0.004Ni2+ mixed with LaTiTaO6: 0.04Cr3+ phosphors have demonstrated their application for spectral analysis. This work provides a new idea for constructing efficient NIR‐II to NIR‐III phosphors.

Glucose metabolism plays a pivotal role in physiological processes and cancer growth. The final stage of glycolysis, converting phosphoenolpyruvate (PEP) into pyruvate, is catalyzed by the pyruvate kinase (PK) enzyme. Whereas PKM1 is mainly expressed in cells with high energy requirements, PKM2 is preferentially expressed in proliferating cells, including tumor cells. Structural analysis of PKM1 and PKM2 is essential to design new molecules with antitumoral activity. To understand their structural dynamics, we performed extensive high‐resolution molecular dynamics (MD) simulations using adaptive sampling techniques coupled to the polarizable AMOEBA force field. Performing more than 6 µs of simulation, we considered all oligomerization states of PKM2 and propose structural insights for PKM1 to further study the PKM2‐specific allostery. We focused on key sites including the active site and the natural substrate Fructose Bi‐Phosphate (FBP) fixation pocket. Additionally, we present the first MD simulation of biologically active PKM1 and uncover important similarities with its PKM2 counterpart bound to FBP. We also analysed TEPP‐46’s fixation, a pharmacological activator binding a different pocket, on PKM2 and highlighted the structural differences and similarities compared to PKM2 bound to FBP. Finally, we determined potential new cryptic pockets specific to PKM2 for drug targeting.

Warburg effect, generates increased demand of glucose in cancer but is relatively underexplored phenomenon in existing commercial anti‐cancer drugs. Here, we present a Ru(II)‐bis‐bipyridyl‐morphocumin complex (2) encapsulated in a self‐assembling glucose‐functionalized co‐polymer P(G‐EMA‐co‐MMA) (where G = glucose; MMA = methyl methacrylate; EMA = ethyl methacrylate), designed to exploit Warburg effect and enhance cancer selectivity. The P(G‐EMA‐co‐MMA) polymer, synthesized via reversible‐addition fragmentation chain transfer (RAFT) polymerization, has a number average molecular weight (Mn, NMR) of 8000 g/mol. Complex 2, stable in aqueous media, selectively releases a cytotoxic, lysosome‐targeting compound morphocumin in the presence of excess H2O2, a reactive oxygen species (ROS) prevalent in tumor microenvironments. Complex 2 promotes ROS accumulation enhancing morphocumin release through a synergistic domino effect. Comparatively, 2 outperforms its curcumin Ru(II) complex (1) in solution stability, organelle specificity, and cellular mechanisms. Both 1 and 2 exhibit phototherapeutic effects under low‐intensity visible light, but their dark toxicity surpasses their photoactivity, highlighting they are superior as chemotherapeutic agents. Complex 2 induces apoptosis via mitochondrial pathway with 9‐fold increase in selectivity for pancreatic cancer cells (MIA PaCa‐2) over non‐cancerous HEK293 cells when delivered encapsulated in glucose‐conjugated polymer (DP@2)activity enhance further 5‐fold by glucose deprivation underscoring their potential in targeted cancer therapy.

Light‐driven molecular rotary motors convert the energy of absorbed light into unidirectional rotational motion and are key components in the design of molecular machines. The archetypal class of light‐driven rotary motors is chiral overcrowded alkenes, where the rotational movement is achieved through consecutive cis‐trans photoisomerization reactions and thermal helix inversion steps. While the thermal steps have been rather well understood by now, our understanding of the photoisomerization reactions of overcrowded alkene‐based motors still misses key points that would explain the striking differences in operation efficiency of the known systems. Here, we employ quantum‐chemical calculations and nonadiabatic molecular dynamics simulations to investigate the excited‐state decay and photoisomerization mechanism in a prototypical alkene‐based first‐generation rotary motor. We show that the initially excited bright state undergoes an ultrafast relaxation to multiple excited‐ state minima separated by low energy barriers and reveal a slow picosecond‐timescale decay to the ground state, which only occurs from a largely twisted dark excited‐state minimum, far from any conical‐intersection point. Additionally, we attribute the origin of the high yields of forward photoisomerization in our investigated motor to the favorable topography of the ground‐state potential energy surface, which is controlled by the conformation of the central cyclopentene rings.

Despite the significant interest in designing artificial ion channels, there is limited availability of channel‐forming molecules to tackle complex issues, especially in biological systems. Moreover, a major challenge is the scarcity of chloride transporters that can selectively induce toxicity in cancer cells while minimizing harm to normal healthy cells. This work reports a series of 2‐hydroxyphenyl benzamide‐based small molecules 1a−1c, which self‐assemble to form barrel rosette‐type artificial ion channels that selectively transport chloride ions across membranes. The formation of these ion channels primarily relies on intermolecular hydrogen bonding and π‐π stacking interactions, as supported by the analysis of single‐crystal X‐ray diffraction and molecular dynamics (MD) simulations. Importantly, chloride ion transport by these compounds specifically triggers apoptosis in cancer cells while demonstrating relatively low toxicity toward non‐cancerous cell lines.

We report the synthesis and characterization of sulfated pillar[5]arene hosts (P5S2 – P5S10) that differ in the number of sulfate substituents. All five P5Sn hosts display high solubility in water (73 – 131 mM) and do not undergo significant self‐association according to 1H NMR dilution experiments. The x‐ray crystal structures of P5S6, P5S6•Me6HDA, P5S8•Me6HDA, and P5S10•Me6HDA reveal one intracavity molecule of Me6HDA and several external molecules of Me6HDA which form a network of close methonium•••sulfate interactions. The thermodynamic parameters of complexation between P5Sn and the panel of guests was measured by direct or competitive isothermal titration calorimetry. We find that the binding free energy toward a guest becomes more negative as the number of sulfate substituents increase. Conversely, the binding free energy of a specific sulfated pillar[5]arene toward a homologous series of guests becomes more negative as the number of NMe groups increases. The ability to tune the host•guest affinity by changing the number of sulfate substituents will be valuable in supramolecular polymers, separation materials, and latching applications.

Rechargeable zinc‐air batteries (RZABs) are considered as one of the most promising clean energy device due to their abundant resources, low cost and environmental friendliness. However, their energy efficiency and cycle life are far from satisfactory due to the poor activity and stability of bi‐functional electrocatalyst in air cathode. In this work, an efficient bi‐functional catalyst (rGO‐CoFe2O4/Co) was derived from its precursor (rGO‐CoFe2O4) through a simple annealing process. Electrochemical measurements prove that rGO‐CoFe2O4/Co with the in‐situ formed Co nano particles and rich oxygen vacancies appears excellent oxygen reduction reaction and oxygen evolution reaction catalytic activity compared to its counterpart. Its half‐wave potential is 0.81 V (vs RHE) and the OER overpotential is only 310 mV (vs RHE). In addition, rechargeable zinc‐air batteries assembled with rGO‐CoFe2O4/Co show the highest peak power density (128.9 mW cm⁻²) and cycling stability compared to rGO‐CoFe2O4 and commercial Pt/C‐RuO2 catalysts. This work provides a simple strategy for the design of advanced bifunctional catalysts.

We present a series of six hypervalent bismuth complexes Bi(R1PDPR2)X bearing ligands characterized by the pyridine‐2,6‐bis(pyrrolide) (PDP) structural motif. While bismuth holds considerable potential for facilitating efficient intersystem crossing (ISC), reports on phosphorescent molecular bismuth complexes are still scarce and mostly based on systems that exhibit inter‐ or intraligand charge transfer character of their optical excitations. Herein, the UV/vis absorptive, luminescent, and electrochemical properties of complexes Bi(R1PDPR2)X are explored, where the substituents R1 and R2, as well as the halide ligand X are varied. These compounds are characterized by an intense HOMO→LUMO transition of mixed ligand‐to‐metal charge transfer (LMCT) and interligand charge transfer (LL'CT) character, as shown by time‐dependent density functional theory (TD‐DFT) calculations. At 77 K in a 2‐MeTHF matrix, these compounds exhibit red, long‐lived phosphorescence with lifetimes ranging from 479 to 14 μs. Cyclic voltammetry measurements and TD‐DFT calculations show that the substituents influence HOMO and LUMO energies to almost equal extent, resulting in nearly constant emission wavelengths throughout this series. Single‐crystal X‐ray diffraction studies of four of the six complexes exemplify the inherent Lewis acidity of the coordinated Bi³⁺ ion, in spite of its hypervalency.

Phthalocyanines are versatile photodynamic therapy agents whose biological activity depends on their aggregation state, which is expected to be influenced by binding to biomolecules. Here, guanine‐rich nucleic acid binding of a water‐soluble cationic, regiopure C4h zinc phthalocyanine bearing four triethylene glycol methyl ether and four N‐methyl‐4‐pyridinium substituents (1) is reported. In contrast to double‐stranded DNA, guanine systems GpG, (GG)10, poly(G) and quadruplex DNA are shown to effectively disrupt phthalocyanine aggregates in buffered solution. This process is accompanied by evolution of the Q‐band absorbance and enhanced emission. Increasing the sequence length from GpG to (GG)10 increases the binding and confirms the importance of multiple binding interactions. Enhanced binding in the presence of KCl suggests the importance of nucleobase hydrogen‐bonded mosaics in phthalocyanine binding. Notably, the (GT)10 sequence is even more effective than quadruplex and pure guanine systems at disrupting the aggregates of 1. Significant time‐dependent binding of 1 with poly(G) reveals biexponential binding over minutes and hours, which is linked to local conformations of poly(G) that accommodate monomers of 1 over time. The study highlights the ability of biomacromolecules to disrupt phthalocyanines aggregates over time, which is an important consideration when rationalizing photoactivity of photosensitizers in‐vivo.

Polyfluoroaryl ethers represent an important framework of biologically active molecules and materials. Owing to the strong bond dissociation energy of C−F bond, selectivity and other issues, transition metal‐catalyzed synthesis of polyfluoroaryl ethers from perfluoroarenes via the activation of C−F bond is challenging and underdeveloped, as compared to the well‐documented C−O bond formation starting from aryl iodides, aryl bromides or aryl chlorides. Herein, an unprecedented Pd‐catalyzed defluorinative etherification for the synthesis of polyfluoroaryl ether skeletons using hydrobenzoxazoles as phenol surrogate, has been reported. The substrate scope for this protocol is broad, with respect to hydrobenzoxazoles and perfluoroarenes, under mild reaction conditions. More importantly, challenging alkenyl and alkynyl substituted polyfluoroarenes could be successfully used as the cou‐pling component for Pd‐catalyzed etherification reaction. Density functional theory (DFT) calculations were employed to investigate the reaction mechanism, which suggested that oxidative addition between polyfluorobenzene and Pd(0) constituted the rate‐determining step.

Polycyclic conjugated hydrocarbons have acquired increased interests recently because of their potential applications in electronic devices. On metal surfaces, the selective synthesis of four‐ and five‐membered carbon rings remains challenging due to the presence of diverse reaction pathways. Here, utilizing the same precursor molecule, we successfully achieved substrate‐controlled highly selective cycloaddition reactions towards four‐ and five‐membered carbon rings. A 97% yield for four‐membered carbon rings on Au(111), while a 96% yield towards five‐membered carbon rings is achieved on Ag(111). The detailed topological structures of the reaction products are carefully examined by bond‐resolving scanning tunneling microscopy (BR‐STM) imaging with a CO functionalized tip. The underlying mechanism of the novel surface‐directed reaction selectivity is elucidated by extensive density functional theory (DFT) calculations. Our study paves the way for high selective synthesis of polycyclic conjugated hydrocarbons with non‐benzenoid rings.

Herein, we describe a stereoselective Ni‐catalyzed N‐glycosylation of glycals. The reaction is enabled by addition of an in situ generated nickel hydride across an olefin prior to C–N bond‐formation. Stereodivergence can be accomplished on kinetic or thermodynamic grounds, thus giving access to either α‐ or β‐N‐glycosides with equal ease. The protocol is distinguished by its operational simplicity, generality and exquisite selectivity, thus offering a new gateway to expedite the synthesis of N‐glycosides.

Deep ultraviolet (DUV) nonlinear optical (NLO) crystals with balanced performance are crucial for extending laser wavelengths into the DUV region, essential for various laser applications. However, developing ideal DUV crystals is challenging due to stringent requirements: strong second‐harmonic generation (SHG) response, short cut‐off wavelength, and effective phase‐matching behavior. DUV NLO borates, which feature π‐conjugated groups, have garnered attention for their higher SHG coefficients compared to phosphates. However, phosphates typically show short UV cut‐off edges due to the large HOMO‐LUMO gap (approximately 9.6 eV) of the [PO₄] units. To enhance the SHG effect while maintaining DUV transparency in phosphates, several strategies have been proposed: 1) using distorted polymerized P−O groups like isolated C₁‐[P₃O₁₀]⁵⁻ and [P₂O₇]⁴⁻; 2) aligning isolated [PO₄]³⁻ tetrahedra along the polar screw axis; 3) introducing additional NLO‐active units; and 4) exploring new units derived from [PO₄]³⁻, such as [PO₃F]²⁻ tetrahedra. These strategies have led to the successful development of various non‐centrosymmetric phosphates, highlighting their potential as DUV NLO candidates. This review explores the relationship between their crystal structures and DUV NLO performance, and proposes future directions for developing ideal DUV NLO materials.

The synthesis of biaryl amides, which are prevalent motifs in bioactive molecules, often necessitates lengthy and inefficient procedures. To address these limitations, catalytic C−H activation protocols have emerged, enabling the direct ortho‐arylation of aryl amides. However, these protocols often suffer from issues such as lack of selectivity, reliance on stoichiometric oxidants, and the requirement for excess reagents and harsh reaction conditions. To overcome these challenges, we present a novel and highly selective protocol for the ortho‐arylation of N‐aryl amides and ureas. The high selectivity originates from the directed installation of BBr3 to form a boracycle, which then undergoes cross‐coupling with an aryl halide. Our method offers significant advantages, including mild reaction conditions, excellent site‐specificity, and scalability. The protocol demonstrates broad compatibility with a diverse range of readily accessible functionalized anilides and aryl iodides, as evidenced by 55 successful examples yielding products in the 30–95 % range. Furthermore, our methodology surpasses conventional approaches by facilitating the one‐pot selective diagonal diarylation of dianilides. This capability unlocks the construction of previously unattainable diagonal aryl systems, which serve as valuable precursors for the synthesis of diagonal tetraarylbenzenediamines and N‐doped fulminenes, two crucial compound classes in materials science.

Two‐photon absorption (TPA) has attracted growing attention over recent years owing to the wide range of applications in organic nonlinear optical (NLO) materials. The quantitative sensitivity of a two‐photon molecular entity is determined by its TPA cross‐section (δTPA). Perylene diimides (PDIs) are excellent n‐type organic semiconductor materials demonstrating distinguished thermal, optical, and chemical stability. Nonetheless, PDIs‐based scaffolds exhibit poor δTPA in the NIR−I region (700–900 nm) due to the lack of suitable molecular design. Here, two novel star‐shaped PDIs fluorophores, namely PDI−S and PDI−Se, were constructed by four periphery S/Se‐fused PDIs connected with bicarbazole core. PDI−S manifested excellent δTPA of 3775 GM, which are among the highest values reported for PDIs excited in the NIR−I region.

Liquid‐crystallization‐driven self‐assembly (LCDSA) has recently emerged as an efficient strategy to create uniform one‐dimensional (1‐D), 2‐D and 3‐D nanostructures in a controlled manner. However, the examples of generation of uniform multi‐morphology nanostructures from solution self‐assembly of one single polymer sample are rare. Herein, we report the first example of preparation of multi‐morphology fried‐egg‐like nanostructures consisting of an inner spherical/bowl‐like core of uniform size and platelets protruded from the core by LCDSA of PAMAM‐Azo6 (PAMAM=polyamidoamine, Azo=azobenzene) in methanol. It is disclosed that the different aggregation rates for PAMAM‐Azo6 with varying contents of Azo units spontaneously separated nucleation and growth stages, which led to the formation of inner spherical/bowl‐like cores (“seeds”) firstly, followed by the formation of platelets protruded from the edges of inner core to give “imperfect” fried‐egg‐like nanostructures. Additional annealing of initially formed “imperfect” fried‐egg‐like micelles will promote the rearrangement of Azo units to give thermodynamically‐favored “perfect” fried‐egg‐shaped micelles with a uniform dimension both in the core and whole structure. This work not only provides an efficient strategy to create uniform multi‐morphology fried‐egg‐shaped nanostructures, but also reveals the essential impact of aggregation kinetics of liquid‐crystalline‐coil BCPs in the formation of multi‐morphology nanostructures.