2D Titania–Carbon Superlattices Vertically Encapsulated in 3D Hollow Carbon Nanospheres Embedded with 0D TiO2 Quantum Dots for Exceptional Sodium‐Ion Storage

Two‐dimensional (2D) superlattices offer promising technological opportunities in tuning the intercalation chemistry of metal ions. Now, well‐ordered 2D superlattices of monolayer titania and carbon with tunable interlayer‐spacing are synthesized by a molecularly mediated thermally induced approach. The 2D superlattices are vertically encapsulated in hollow carbon nanospheres, which are embedded with TiO₂ quantum dots, forming a 0D‐2D‐3D multi‐dimensional architecture. The multi‐dimensional architecture with the 2D superlattices encapsulated inside exhibits a near zero‐strain characteristic and enriched electrochemical reactivity, achieving a highly efficient Na⁺ storage performance with exceptional rate capability and superior long‐term cyclability.     

Manipulating the Stacking of Triplet Chromophores in the Crystal Form for Ultralong Organic Phosphorescence

Provided here is evidence showing that the stacking between triplet chromophores plays a critical role in ultralong organic phosphorescence (UOP) generation within a crystal. By varying the structure of a functional unit, and different on‐off UOP behavior was observed for each structure. Remarkably, 24CPhCz, having the strongest intermolecular interaction between carbazole units exhibited the most impressive UOP with a long lifetime of 1.06 s and a phosphorescence quantum yield of 2.5 %. 34CPhCz showed dual‐emission UOP and thermally activated delayed fluorescence (TADF) with a moderately decreased phosphorescence lifetime of 770 ms, while 35CPhCz only displayed TADF owing to the absence of strong electronic coupling between triplet chromophores. This study provides an explanation for UOP generation in crystal and new guidelines for obtaining UOP materials.     

Effects of different oxygen-containing anions on the structure of water clusters

Using Ni(Im)₆²⁺ (Im = imidazole) as the structural unit, the effects of oxygen-containing anions, such as SO₄^2-, NO₃^? and CO₃^2- on the structure of water clusters were studied. The crystal structures of three compounds [Ni(Im)₆][SO₄(H₂O)₁₁] (1), [Ni(Im)₆][(NO₃)Cl(H₂O)₄] (2), and [Ni(Im)₆][CO₃(H₂O)₅] (3) were obtained. Using Mercury-3.8 software to analyze the above three crystal structures, find different anion of water clusters had a significant effect on the supramolecular structure. At the same time, it also significantly influences the number of water molecules in the crystal structure.     

Highly stable polyoxometalate‐resorcin[4]arene‐based inorganic‐organic complexes for catalytic oxidation desulfurization

Self‐assembly of a resorcin[4]arene‐based ligand (TMR4A) with metal salts and H₃PMo₁₂O₄₀·xH₂O offers two isostructural complexes, namely, [Ni₂Cl(TMR4A)₂(CH₃CN)₂]·[PMo₁₂O₄₀]·4CH₃CN ( 1 ) and [Co₂Cl(TMR4A)₂(CH₃CN)₂]·[PMo₁₂O₄₀]·4CH₃CN ( 2 ). In both 1 and 2 , one Cl^? anion bridges two metal cations, and each metal cation is further chelated by four 2‐mercaptopyridine N‐oxide groups of one TMR4A, producing a [M₂Cl(TMR4A)₂]³⁺ dimer (M = Ni or Co). The negative [PMo₁₂O₄₀]^3? as a counter‐anion balances the positive charge. Markedly, 1 and 2 exhibit high stability in aqueous solutions with different pH values and in organic solvents. Remarkably, the efficient heterogeneous catalytic capability for oxidative desulfurization was studied by suing 1 and 2 as recycled catalysts. Moreover, the electrochemical behaviors of the two compounds were discussed as well.     

A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design

A novel niobium oxyiodate sulfate, Nb₂O₃(IO₃)₂ (SO₄), was fabricated by a rational multi‐component design under moderate hydrothermal conditions. This multi‐component design is inspired by an interesting niobium oxysulfate reaction, which opens a new door for synthetic method to effectively introduce refractory metals such as Nb into crystal structures by hydrothermal synthesis. Nb₂O₃(IO₃)₂(SO₄) features a cube‐like topological structure with a large phase‐matching second harmonic generation (SHG) response (6×KDP), a wide transparency window (0.38–8 μm), and a high laser damage threshold (LDT) (20×AgGaS₂). It has the highest thermostability (stable up to 580 °C under air) among reported non‐centrosymmetric (NCS) iodates and sulfates and is stable in water and even concentrated H₂SO₄. Furthermore, Nb₂O₃(IO₃)₂(SO₄) is a unique nonlinear optical (NLO) material among iodates and sulfates, because its SHG effect is mainly caused by the MO₆ units rather than the IO₃ or SO₄ units, which is demonstrated by density functional theory (DFT) calculations.     

Bio‐Inspired Stable Lithium‐Metal Anodes by Co‐depositing Lithium with a 2D Vermiculite Shuttle

Progress in lithium‐metal batteries is severely hindered by lithium dendrite growth. Lithium is soft with a mechanical modulus as low as that of polymers. Herein we suppress lithium dendrites by forming soft–hard organic–inorganic lamella reminiscent of the natural sea‐shell material nacres. We use lithium as the soft segment and colloidal vermiculite sheets as the hard inorganic constituent. The vermiculite sheets are highly negatively charged so can absorb Li⁺ then be co‐deposited with lithium, flattening the lithium growth which remains dendrite‐free over hundreds of cycles. After Li⁺ ions absorbed on the vermiculite are transferred to the lithium substrate, the vermiculite sheets become negative charged again and move away from the substrate along the electric field, allowing them to absorb new Li⁺ and shuttling to and from the substrate. Long term cycling of full cells using the nacre‐mimetic lithium‐metal anodes is also demonstrated.     

Activation of Prodrugs by NIR‐Triggered Release of Exogenous Enzymes for Locoregional Chemo‐photothermal Therapy

Enzymes have been used to direct the conversion of prodrugs in cancer therapy. However, non‐specific distribution of endogenous enzymes seriously hinders their bioapplications. Herein, we developed a near‐infrared‐triggered locoregional chemo‐photothermal therapy based on the exogenous enzyme delivery and remolded tumor mivroenvironment. The catalytic efficiency of enzymes was enhanced by the hyperthermia, and the therapeutic efficacy of photothermal therapy (PTT) was improved owing to the inhibition of heat shock protein 90 by chemotherapeutics. The locoregional chemo‐phototherapy achieved a one‐time successful cure in 4T1 tumor‐bearing mice model. Thus, a mutually reinforcing feedback loop between PTT and chemotherapy can be initiated by the irradiation, which holds a promising future in cancer therapy.     

Designed Synthesis of a 2D Porphyrin‐Based sp2 Carbon‐Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis

The construction of stable covalent organic frameworks (COFs) for various applications is highly desirable. Herein, we report the synthesis of a novel two‐dimensional (2D) porphyrin‐based sp² carbon‐conjugated COF (Por‐sp²c‐COF), which adopts an eclipsed AA stacking structure with a Brunauer—Emmett—Teller surface area of 689 m² g^?1. Owing to the C=C linkages, Por‐sp²c‐COF shows a high chemical stability under various conditions, even under harsh conditions such as 9 m HCl and 9 m NaOH solutions. Interestingly, Por‐sp²c‐COF can be used as a metal‐free heterogeneous photocatalyst for the visible‐light‐induced aerobic oxidation of amines to imines. More importantly, in comparison to imine‐linked Por‐COF, the inherent structure of Por‐sp²c‐COF equips it with several advantages as a photocatalyst, including reusability and high photocatalytic performance. This clearly demonstrates that sp² carbon‐linked 2D COFs can provide an interesting platform for heterogeneous photocatalysis.     

Novel coumarin-based containing denrons selective fluorescent chemosesor for sequential recognition of Cu2+ and PPi

In this study, we have successfully synthesized a novel coumarin-based dendrons derivative CD and its chemical structure was characterized by ¹H NMR, ¹³C NMR and ESI-HR-MS. The sensor CD showed an obvious “on-off” fluorescence quenching response toward Cu²⁺ with a maximum quenching efficiency of 99.8%. The CD-Cu²⁺ complex showed an “off-on” fluorescence enhancement response toward PPi over many competitive anions. The detection limit of the sensor CD was 0.29?×?10^?6?M to Cu²⁺ and 2.39?×?10^?9?M to PPi. In addition, the sensor CD showed a 1:1 binding stoichiometry to Cu²⁺ and the sensor CD-Cu²⁺ showed a 2:1 binding stoichiometry to PPi in CH₃CN/HEPES buffer medium (9:1 v/v, pH?=?7.2). The stable pH range of sensor CD to Cu²⁺ and CD-Cu²⁺ to PPi was from 3 to 8.