CrystEngComm最新文献

Hierarchical metal–organic frameworks (MOFs) and their derivatives are categorized into three structural types: hierarchical porous structure, hierarchical architectural structure, and hierarchical compositional structure. With their structural diversity and ability to synergistically regulate electrochemical properties across multiple scales, hierarchical MOF materials have attracted widespread attention. This review systematically analyzes strategies for the three types of hierarchical MOFs and their derivatives, including the template guided method, additive-assisted modulation, etching, ion-exchange, self-assembly, and the in situ growth method. Recent applications of MOFs and their derivatives in electrochemical energy storage devices, including secondary batteries and supercapacitors, are also introduced. Finally, the structural advantages, challenges, and future research prospects of hierarchical MOFs and their derivatives are summarized.

Solar desalination technology is the cleanest and lowest energy-consuming way to produce fresh water. Nevertheless, the low vapor generation rate of unmodified evaporation membranes limits their practical applications. Herein, an evaporator with three-dimensional water-storage microcapsules and a tungsten nitride (WN) bionic flower-like structure composite (WN@NC) was prepared by combining tungsten nitride (WN) nanoparticles with carbon. WN has high light absorption efficiency, while the porous channels inside the NC enable incident light to be reflected and absorbed multiple times within. Benefiting from the synergistic effect between the porous channels of flower-like NC and the light absorption capacity of WN, WN@NC achieves a high light absorption efficiency of 98.7% in the infrared light region, the main heat-generating band. As a result, the evaporator achieves a vapor generation rate of 1.82 kg m⁻² h⁻¹ and an energy utilization efficiency of 96.5%. The continuous evaporation test lasting for 7 days still maintains an average daily vapor generation rate of 8.2 kg m⁻². This study provides a new strategy for further improving the vapor generation rate of solar interfacial evaporators.

The tunability of ferroelectric properties is highly desirable for applications in optoelectronic devices, memories, and sensors. Although mixing ferroelectric and nonferroelectric molecules is a common approach for adjusting their ferroelectric properties, the generation of ferroelectric phases by mixing two different nonferroelectric molecules is rare. In this study, we present ferroelectric mixtures composed of pyroelectric (nonswitchable) crystal and liquid (nonelectroresponsive) compounds, the former and the latter of which are N,N′-bis(3,4-dialkoxyphenyl)ureas with (S)-citronellyl (U-3,4-Scit) and (rac)-2-ethylhexyl (U-3,4-b8) groups. The packing structures in the crystal phase of the binary mixtures differed from that of the pure pyroelectric compound. Furthermore, increasing the molar ratio of the liquid compound decreased the intermolecular hydrogen bonding strength and caused alkyl chain disordering in the crystal phase. Therefore, the pyroelectric nature of the single component changed to a ferroelectric nature due to enhanced responsiveness under an electric field. The mixture with a molar ratio of U-3,4-b8 of 0.3 exhibited the highest spontaneous polarization of approximately 1400 nC cm⁻² and a coercive field of 9 V μm⁻¹ at 45 °C. Mixing these compounds successfully tuned the spontaneous polarization, coercive field, and temperature range of ferroelectric soft crystals, and this result provides new insights into the design of ferroelectrics.

The low-temperature catalytic oxidation activity of cobalt oxide (Co₃O₄) is effectively enhanced by metal doping. A series of Cu/Mn co-doped Co₃O₄ catalysts with controlled doping ratios were synthesized via co-precipitation and subsequently evaluated for carbon monoxide (CO) oxidation. The optimal low-temperature activity was achieved at a Cu/Mn ratio of 0.35/0.65, with the catalyst also demonstrating robust stability. Combined characterization results (XRD, FT-IR, XPS, H₂-TPR, and O₂-TPD) reveal that Cu/Mn co-doping weakens Co–O bonding and enhances low-temperature reducibility and oxygen mobility, thereby generating abundant surface oxygen defects. These defects facilitate the activation of molecular oxygen (O₂), thereby increasing CO conversion at low temperatures. This research provides valuable insights into the development of highly efficient catalysts for CO oxidation.

Considering the geological abundance, stability, and pivotal role of nesquehonite (MgCO₃·3H₂O) within the MgO–CO₂–H₂O system, this review highlights key aspects of this hydrated magnesium carbonate. These include its synthesis process, crystal morphology, the influence of additives, thermal stability, high-pressure behavior, combined effects of pressure and temperature, as well as insights into hydrogen bonding in nesquehonite and related basic and hydrated carbonates. Finally, the review discusses the potential practical applications of nesquehonite. We conclude that an integrated experimental and theoretical approach provides a clear and accessible framework for understanding nesquehonite's structure, properties, and phase behavior, thereby offering valuable insights to guide further research across multiple scientific disciplines.

The subcellular organelle-targeted delivery strategy appears to be an effective method to induce drug accumulation in the desired sites for enhanced therapeutic efficacy. However, insufficient lysosomal escape constitutes a major barrier to the efficient delivery of drugs to targeted tissues. Mitochondria-targeted drug delivery systems (DDSs) have emerged as a promising alternative and attract considerable research interest. However, sophisticated post-modification procedures are a prerequisite for acquiring the mitochondria-targeted feature, resulting in far too much complexity to achieve effective performance. Herein, mitochondria-targeted calcium carbonate hollow nanospheres were easily synthesized just by the regulation of lotus pollen extract. The biomolecules in lotus pollen extract not only regulate the morphology and structure of calcium carbonate, but also endow it with an excellent mitochondria-targeted property. The hollow calcium carbonate nanospheres exhibit remarkable capability for drug loading, and DOX loading entrapment was calculated to be 85.80%. The co-localization analysis of Pearson's correlation factor also proves the good lysosomal escape and mitochondria-targeted characteristics of this system. Furthermore, the drug in this mitochondria-targeted drug delivery system shows pH-dependent and sustained-release behavior at the tumor site, which significantly augments the apoptosis-inducing effect. This work may provide a helpful reference for the design and synthesis of subcellular organelle-targeted DDSs.

In this article, we report the synthesis, spectroscopic and X-ray characterization of two fluorinated 2′-hydroxychalcone derivatives (E)-3-(4-fluorophenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one (1) and (E)-1-(2-hydroxyphenyl)-3-[(4-trifluoromethyl) phenyl]prop-2-en-1-one (2). These compounds were synthesized by Claisen–Schmidt condensation between 2′-hydroxyacetophenone and 4-fluorobenzaldehyde and 4-(trifluoromethyl)benzaldehyde under basic conditions to afford the desired compounds in good yields. The structures were fully established using FTIR, UV-visible and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The crystallographic analysis reveals that the supramolecular assembly in 1 is mainly governed by C–H⋯O and C–H⋯F H-bonds and C–H⋯O, F⋯F, and π-stacking interactions were observed in 2. Hirshfeld surface analysis revealed that H⋯H, H⋯O/O⋯H and H⋯F/F⋯H contacts dominate the crystal packing of both compounds. Lattice and intermolecular interaction energies for 1, 2, and two related compounds were computed by using the PIXEL procedure. Contact enrichment ratios showed the most favorable intermolecular interactions for all the four compounds. A detailed density functional theory (DFT) computational analyses were performed to evaluate the strength and nature of the intermolecular interactions which stabilize the crystal packing. Finally, possible pharmacological effects, mechanisms of action, metabolism-related actions, and toxic effects are predicted using PASSonline software. The four analyzed 2′-hydroxy-chalcones exhibited high anti-hypoxic activity. Pharmacokinetic properties, as well as absorption, distribution, metabolism, excretion and toxicity properties were also predicted using the online SwissADME software.

The effective remediation of radioactive strontium-90 (⁹⁰Sr) from complex aqueous environments remains challenging due to the inherent high solubility and migration propensity of Sr²⁺ ions. Herein, we synthesized hydrothermally a new two-dimensional (2D) crystalline zirconium phosphate fluoride [(CH₃)₂NH₂][Zr(PO₄)F₂] featuring a layered anionic architecture of [Zr(PO₄)F₂]_nⁿ⁻ with intercalated [(CH₃)₂NH₂]⁺ cations, which shows exceptional Sr²⁺ remediation capability. It possesses a high maximum Sr²⁺ adsorption capacity (q^Sr_m) of 161.48 mg g⁻¹ (higher than that of many inorganic crystalline adsorbents) and fast kinetics for Sr²⁺ capture (Sr²⁺ removal rate (R^Sr) of 94.89% within 1 min). Specifically, it maintains Sr²⁺ removal efficiency in the presence of competing Cs⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺ ions and in actual aqueous systems including seawater (R^Sr = 79.06%). X-ray photoelectron spectroscopy (XPS) and thermodynamics confirm that spontaneous Sr²⁺ capture occurs through ion exchange processes, where the interlayered [(CH₃)₂NH₂]⁺ cations in [(CH₃)₂NH₂][Zr(PO₄)F₂] are exchanged with Sr²⁺. The compound [(CH₃)₂NH₂][Zr(PO₄)F₂] represents the first crystalline inorganic zirconium phosphate fluoride ion exchange material for radionuclide capture. This work provides a high-performance ion exchanger as a candidate for radiostrontium capture.

This study presents a comprehensive investigation into the synthesis, structural organization, and optoelectronic properties of meso-tetrakis(4-cyanophenyl)porphyrin (CNP) (1) and its tin(IV) complexes Sn-CNP(IB)₂·2DMF (2) and Sn-CNP(IP)₂·DMF (3) functionalized with axial linkers 4-iodobenzoic acid (IB) and 4-iodophenol (IP), respectively. Crystallographic analysis reveals the packing motifs are stabilized by directional CN⋯H–C hydrogen bonds in all compounds towards the formation of hydrogen bonded frameworks, which are further reinforced by halogen–halogen contacts in compound 3. UV-vis absorption, fluorescence data and electrochemical studies demonstrate that tin(IV) coordination and axial linkers significantly modulate the electronic structure of the porphyrin system. Density functional theory (DFT) and reduced density gradient (RDG) analysis quantify the strength and nature of non-covalent interactions that stabilize supramolecular assemblies. Spectroscopic and theoretical results demonstrate significant modulation of charge-transfer characteristics and band gap energies in response to metalation and axial ligand variation.

Metal halide hybrid materials exhibit significant potential in optoelectronics owing to their tunable band structures, high photoluminescence quantum yields, and structural diversity with tunable topologies. This highlight systematically elaborates on the mechanisms and advances in tuning luminescence properties through an ion regulation strategy. Initially, it deciphers three dominant emission mechanisms, self-trapped exciton (STE) emission, intrinsic defect emission, and characteristic ion emission, highlighting the critical role of electron–phonon coupling strength in modulating STE efficiency. Key strategies include: B-site cation design for spectral tuning; heterometallic co-doping for white-light/excitation-dependent emission; and halide/organic cation synergy to boost radiative efficiency. Applications span stimuli-responsive sensors, efficient electroluminescent devices, high-resolution scintillators, and CPL systems. Future challenges focus on lead-free alternatives, multicomponent structure–property relationships, and device stability for next-gen luminescent materials.