CrystEngComm最新文献

Coordination polymers (CPs) are versatile materials with applications across various fields, including the development of supramolecular electronic devices aimed at harnessing renewable energy sources. In this study, we report the design and synthesis of two one-dimensional (1D) CPs: [Cd(4-avp)₂(mes)(H₂O)]·H₂O (CP1) and [Zn(4-avp)₂(mes)(H₂O)]·H₂O (CP2) constructed using a relatively underexplored, highly conjugated polycyclic aromatic hydrocarbon (PAH)-based monodentate ligand, 4-[2-(9-anthryl)vinyl]pyridine (4-avp), in combination with a linear bidentate linker, mesaconic acid (H₂mes). Both compounds were characterized through elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, and single-crystal X-ray diffraction (SCXRD). Structurally, the Cd(II) or Zn(II) metal centers are bridged by mes ligands to form 1D polymeric chains. The axial sites are coordinated by 4-avp ligands, which engage in π⋯π interactions and promote the formation of higher-dimensional supramolecular networks combining with hydrogen bonding interactions. Remarkably, both CPs display semiconducting properties and function as Schottky barrier diodes. Notably, CP1 demonstrates significantly enhanced electrical conductivity (1.39 × 10⁻³ S m⁻¹), approximately four times higher than that of CP2 (3.71 × 10⁻⁴ S m⁻¹). This improved performance is attributed to the larger Cd(II) ion, which allows greater orbital overlap, thereby facilitating more efficient charge transport. These findings are further supported by band gap calculations using density functional theory (DFT) computation and density of state (DOS) calculations.

Acalabrutinib, an anti-cancer drug, was approved by the USFDA in 2017. However, the acalabrutinib capsules (marketed as CALQUENCE) posed certain challenges for cancer patients. To overcome these issues, the brand company developed acalabrutinib maleate tablets, which received USFDA approval in 2022. While acalabrutinib has multiple solid forms, acalabrutinib maleate salt exists only as a hydrate. This study addressed the literature discrepancy regarding acalabrutinib maleate whether it is a monohydrate or sesquihydrate. It also aimed to develop a novel solid form of acalabrutinib maleate salt with improved or comparable physicochemical properties to meet the unmet needs of cancer patients. This is the first study to report a new solid form, specifically a pharmaceutically acceptable solvate of acalabrutinib maleate, and to conduct its structural investigation. Various analytical tools, including X-ray diffraction (powder XRD and single crystal XRD), spectroscopy (¹H-NMR and HPLC), thermal analyses (DSC and TGA), and physicochemical characterization (solubility and stability), were used to investigate the properties of the new solid form. The physicochemical studies indicated that the new solid form of acalabrutinib maleate has similar solubility to its commercial form and remained stable after a six-month study under FDA-recommended storage conditions. To the best of our knowledge, this is the first time the reason for similar solubility has been linked to isostructurality, using Hirshfeld surface and Xpac analysis. Therefore, the novel, stable, and scalable new solid form discussed in this study is a potential candidate for early market launch due to its similar properties to the commercial form.

Artesunate (ATS), a BCS class II drug widely used for anti-malaria therapy, exhibits not only poor solubility but also poor stability. This study aimed to discover novel multicomponent crystal forms of ATS with improved physicochemical properties. Screening of 117 coformer candidates using mechanochemical solvent drop grinding (SDG) or solvent evaporation (SE) resulted in discovering five novel multicomponent crystal forms of ATS with 4-aminobenzoic acid (ABA), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,2-di(pyridine-4-yl)ethane (DPE), 1,10-phenanthroline (PHEN) and urea (URE). Based on the ΔpK_a rule, FTIR results and structure analyses, these solids are cocrystals except DABCO. Additionally, ATS–URE cocrystals can be crystallised as different solvate forms, including methanol, ethanol, and acetonitrile. Interestingly two crystal forms of 2 : 1 ATS–DABCO have been discovered, i.e., form 1 is cocrystal and form 2 is salt. The crystal structures of these multicomponent ATS crystals were determined by single crystal X-ray diffraction and characterised by powder X-ray diffraction, Fourier transform infrared spectroscopy and different thermal analytical techniques (i.e., differential scanning calorimetry, thermogravimetric analysis and hot stage microscopy). It has been shown that some of the multicomponent ATS crystals can significantly improve the in vitro dissolution performance of ATS and its stability in solution. Unfortunately, the solid-state stability study shows that these multicomponent crystals do not exhibit better stability than the raw ATS under the conditions studied. In conclusion, the discovery of more multicomponent crystals of ATS with improved physiochemical properties (e.g., solubility and/or stability) could help to enhance its therapeutic efficacy.

This review summarizes recent advances in five-coordinate Co(II) single-ion magnets (SIMs) with trigonal bipyramidal and square pyramidal geometries, highlighting the influence of these geometries on magnetic anisotropy and magnetization dynamics. The insights presented in this review provide a strong foundation for the strategic design of ligand environments surrounding the Co(II) center. By understanding the interplay between geometries and electronic structures, researchers can strategically tune the ligand field strength to modulate magnetic anisotropy and exert precise control over the overall magnetic behavior.

Electrocatalytic hydrogen production serves as a clean and efficient energy conversion technology that plays a vital role in achieving sustainable energy supply. However, the energy conversion efficiency in electrocatalytic processes is often limited by complex electrode–electrolyte interfacial behaviors, particularly the influence of interfacial water structures. Recent studies have shown that rational control of interfacial water structures can significantly enhance catalytic performance, although a systematic understanding of the relationship between the water structure and hydrogen evolution performance remains elusive. This review summarized recent advances in the field of interfacial water structure regulation, aiming to reveal how different control strategies affect electrocatalytic hydrogen production performance. We clarified the fundamental characteristics of interfacial water and its critical role in proton transfer kinetics and intermediate adsorption energetics. We then discussed various control strategies in detail, including chemical modification, physical field regulation, nanostructure design and dynamic regulation. Furthermore, this review addressed the current technical challenges and future research directions in interfacial water structure regulation. Through a comprehensive analysis of existing research and an outlook on future development trends, this paper provides new perspectives and ideas for further optimizing the performance of electrocatalytic hydrogen production.

Mono-element 2D materials from group V_A have attracted extensive attention due to their outstanding electronic properties. As a pioneering material in this category, black phosphorene possesses remarkable carrier mobility and a tunable bandgap, showing great promise for high-performance field-effect transistors (FETs). However, its rapid degradation in the ambient atmosphere leads to significant performance deterioration, severely limiting its practical use. In contrast, antimonene, another group V_A member, exhibits exceptional environmental stability, thereby distinguishing itself as a robust alternative for various applications. Nevertheless, the practical deployment of antimonene is hindered by existing synthesis methods, which often require high reaction temperatures, stringent inert atmospheres, and involve toxic thiol-based reagents. To address these challenges, we present an eco-friendly and energy-efficient topochemical reduction conversion route. This approach involves the fabrication of well-defined SbI₃ nanosheet precursors and their subsequent conversion into high-quality antimonene nanosheets via a NaBH₄ reduction process at room temperature. This approach effectively completely eliminates the need for high-energy conditions and toxic reagents, offering a straightforward and reliable strategy for the production of antimonene nanosheets.

Mechanically flexible single crystals are emerging as a useful class of materials due to their unique combination of crystallinity and molecular-scale responses to applied mechanical stress. In this tutorial review, we suggest best practice approaches to the identification and characterisation of these fascinating materials. These approaches can be applied in crystals that show either plastic or elastic flexibility, or a combination of the two. In particular, we highlight that the molecular mechanism of flexibility that occurs when a crystal is subject to mechanical stress varies from system to system and so it is impossible to infer the nature of movement that will occur merely from crystal packing analysis. Understanding the structural changes that occur when a crystal is subject to mechanical stress is essential for developing their utility in a wide range of applications, particularly in optoelectronics, waveguides and piezoelectrics.

This study explores the impact of Ge, In, Pb, and Sb additives on the kinetic behaviors of pre-recrystallization and recrystallization in Se₇₈Te₂₀Sn₂ alloys. Non-isothermal calorimetric experiments were conducted to determine the glass transition temperature (T_g), recrystallization onset temperature (T_o), peak temperature (T_c), and associated activation energies (E_g, E_c). Parameters such as Lasocka's coefficients (A_g, B_g, A_c, B_c), recrystallization rate constant (K), Hruby number (H_r), and thermal stability (S) were evaluated to assess the glass-forming tendencies and resistance to devitrification. Additives significantly influenced T_g, T_c, and E_c, with Sb yielding the highest thermal stability and glass-forming ability. Stability criteria based on the Arrhenius rate constant K(T) highlighted the correlation between configurational changes and energy barriers. These findings offer insights into thermal behavior, enabling the design of tailored glass–ceramic alloys for advanced applications.

It is advantageous to harness the synergistic effect of multiple components to enhance the catalytic performance of integrated nanozymes, mimicking the efficacy of natural enzymes in catalytic processes. Herein, the enzyme-like catalysis of a three-dimensional (3D) Au-decorated MoS₂ nanosheets (NSs) grown in situ on S, N, P, and Fe-doped carbon@MoO₂ substrate derived from rod-like structured MoO₃@Fe-PZS is investigated. Compared with single MoS₂ NSs, the synergistic effects of Au nanoparticle (NP) decoration, S, N, P, and Fe-doped carbon@MoO₂ substrate and 1D open porous structural advantages allow Au–MoS₂/Fe-NPSC@MoO₂ to achieve optimum enzyme-like activity as well as the reduction of 4-nitrophenol(4-NP). In addition, good hydrophilicity of Au–MoS₂/Fe-NPSC@MoO₂ is conducive to achieving rapid mass transport. The test results showed that the composite exhibited excellent peroxidase activity and 4-NP catalytic reduction performance thanks to the synergistic effect of the above components. Therefore, Au–MoS₂/Fe-NPSC@MoO₂ composites have great potential in the development of artificial enzymes with catalytic dynamics of natural enzymes. This research introduces a facile approach for concurrently incorporating structural merits, electrical conductivity, and electronic engineering principles to develop versatile catalyst systems with multifaceted functionalities.

A library of ten complexes, [Yb₂(hfac)₆(L)] (1), [Yb₆(hfac)₁₄(OH)₄(L)₂] (2), [Dy(hfac)₃(L)]₂·C₂H₄Cl₂ ((3)·C₂H₄Cl₂), [Dy(hfac)₃(L)]₂[Dy(hfac)₃(H₂O)₂] (4), [Dy₆(hfac)₁₄(OH)₄(L)₂] (5), [Yb(tta)₃(L)] (6) and [Ln₂(hfc)₆(L)] (Ln = Dy ((−)7, (+)7) and Yb ((−)8, (+)8)) (where hfac⁻ = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta⁻ = 2-thenoyltrifluoroacetylacetonate, hfc⁻ = 3-(heptafluoropropylhydroxymethylene-(±)-camphorate and L = 4-methylbipyrimidine-2-N-oxide ligand)) were isolated and characterized by single crystal and powder X-ray diffraction. All the Yb(III) based-complexes demonstrate a slow relaxation of the magnetization under an applied DC field, which occurs through a Raman process and an additional Orbach process for 6. The two Dy(III) dinuclear complexes 3 and (±)7 display slow magnetic relaxation in a zero applied DC field, whereas complex 4, which is similar to 3 with co-crystallization of Dy(hfac)₃(H₂O)₂, presents only a field-induced slow magnetic relaxation. Multi-field-induced single-molecule magnet (SMM) behaviour was observed for (+)7, while this was not the case for the Yb(III) analogue (+)8.