CrystEngComm最新文献

{"title":"Mechanochemical cocrystallisation in a simplified mechanical model: decoupling kinetics and mechanisms using THz-TDS","authors":"Ruohan Zhang and J. Axel Zeitler","doi":"10.1039/D5CE00625B","DOIUrl":"https://doi.org/10.1039/D5CE00625B","url":null,"abstract":"<p >Mechanical compaction plays a dual role in mechanochemical cocrystallisation, simultaneously influencing reaction rates and crystallisation pathways. Here, we introduce a simplified single-punch compaction model that allows systematic variation of force (5–40 kN) and dwell time under controlled conditions. Using terahertz time-domain spectroscopy (THz-TDS) combined with a dual kinetic fitting strategy (free-fit <em>vs.</em> fixed-<em>n</em> Avrami models), we decouple kinetic rate constants from mechanism changes and map force-dependent transitions in a TPMA–PE cocrystallisation system. Increasing compaction force from 5 kN to 40 kN reduced the fitted rate constant <em>k</em><small>_free</small> from 0.2147 to 0.1195 h<small>^{−<em>n</em>}</small>, while increasing the Avrami exponent <em>n</em><small>_free</small> from 0.6409 to 1.2057. This suggests a force-driven transition from diffusion-limited or heterogeneous nucleation to more interface-controlled one-dimensional crystallisation. These findings provide new mechanistic insight into how mechanical energy inputs shape solid-state transformations, with implications for process optimisation in pharmaceutical manufacturing, especially in continuous production environments where compaction profiles vary dynamically.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6360-6372"},"PeriodicalIF":2.6,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00625b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Establishing σ-hole tetrel bonds by hemidirected lead(ii) phosphonodithioates","authors":"Pretam Kumar, Rosa M. Gomila, Antonio Frontera and Sushil K. Pandey","doi":"10.1039/D5CE00611B","DOIUrl":"https://doi.org/10.1039/D5CE00611B","url":null,"abstract":"<p >This study explores the ability of hemidirected lead(<small>II</small>) centres to form σ-hole tetrel bonds (TtBs) with electron-rich atoms. Lawesson's reagent was used to produce arylphosphonodithioates and their corresponding lead(<small>II</small>) complexes with the formulas (4-C<small>₆</small>H<small>₄</small>OMe){4-CH<small>₃</small>C<small>₆</small>H<small>₄</small>O}PS<small>₂</small>NHEt<small>₃</small> (<strong>1</strong>), (4-C<small>₆</small>H<small>₄</small>OMe){4-CH<small>₃</small>C<small>₆</small>H<small>₄</small>O}PS<small>₂</small>Na (<strong>2</strong>), and Pb[S<small>₂</small>P{OC<small>₆</small>H<small>₄</small>(4-CH<small>₃</small>)}{C<small>₆</small>H<small>₄</small>(4-OCH<small>₃</small>)}]<small>₂</small> (<strong>3</strong>). The molecular structures were studied by X-ray crystallography, revealing that <strong>1</strong> crystallizes in the orthorhombic crystal system with the <em>P</em>2<small>₁</small>2<small>₁</small>2<small>₁</small> space group and <strong>3</strong> in the monoclinic crystal system with the <em>P</em>2<small>₁</small>/<em>c</em> space group. In complex <strong>3</strong>, the Pb(<small>II</small>) center exhibits a hemidirected coordination sphere, bonded to three sulfur atoms and possesses a stereochemically active lone pair, resulting in a distorted trigonal pyramidal geometry. The presence of bulky ligands in complex <strong>3</strong> limits its coordination, generating an open region around Pb that facilitates the formation of directional σ-hole TtBs, specifically Pb⋯S and Pb⋯π interactions. Molecular electrostatic potential (MEP) analysis reveals a pronounced σ-hole at the Pb center, which facilitates directional TtBs. These interactions were further characterized and energetically evaluated using quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) plot analyses. The supramolecular architecture of complex <strong>3</strong> features a self-assembled dimer stabilized by Pb⋯S TtBs, forming an eight-membered quasi-cyclic motif. Additionally, Hirshfeld surface analysis (HSA) highlights the role of TtBs and other non-covalent contacts in the crystal packing of complex <strong>3</strong>. Overall, this work underscores the importance of σ-hole interactions in the design and assembly of Pb(<small>II</small>)-based coordination complexes and provides valuable insights for advancing supramolecular and crystal engineering strategies in modern coordination chemistry.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6386-6396"},"PeriodicalIF":2.6,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aliovalent Al3+ substituted ultra-wide bandgap CuAlX4 (X = Cl, Br) for infrared nonlinear optics","authors":"Sheng Lv, Liangcheng Song, Yanling Xu, Hongyan Cui, Chongqiang Zhu and Chunhui Yang","doi":"10.1039/D5CE00573F","DOIUrl":"https://doi.org/10.1039/D5CE00573F","url":null,"abstract":"<p >The development of high-performance infrared (IR) nonlinear optical (NLO) crystals with ultra-wide bandgaps (&gt;4.0 eV) is crucial for advancing laser technologies, yet achieving a balance between wide bandgaps and strong NLO responses remains challenging. A trivalent aliovalent substitution strategy is reported in this work to engineer diamond-like (DL) halides, CuAlX<small>₄</small> (X = Cl, Br), which simultaneously achieve record-wide bandgaps (4.25 eV for CuAlCl<small>₄</small> and 4.09 eV for CuAlBr<small>₄</small>), high laser-induced damage threshold (LIDT) values (46.2 MW cm<small>⁻²</small> and 33.9 MW cm<small>⁻²</small>, respectively), and competitive second-harmonic generation (SHG) coefficients (3.52 pm V<small>⁻¹</small> and 7.12 pm V<small>⁻¹</small> at 2.09 μm, respectively). Structural characterization and first-principles calculations reveal that the introduction of Al<small>³⁺</small> induces asymmetric [CuX<small>₄</small>] tetrahedra and cationic vacancies, breaking inversion symmetry and enhancing hyperpolarizability. The synergistic effects of increased valence electron concentration and optimized tetrahedral alignment result in exceptional optical properties, including broad transparency and type-I phase-matching behavior. This work demonstrates the potential of high-valence substitution for designing DL halides with ultra-wide bandgaps and robust NLO performance, offering new insights for IR optoelectronic applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6202-6212"},"PeriodicalIF":2.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanical characterization of synthesized hierarchical porous silver through impact analysis of dealloying temperature on ligament morphology","authors":"Yikai Sun, Zaijiu Li and Qinglin Jin","doi":"10.1039/D5CE00641D","DOIUrl":"https://doi.org/10.1039/D5CE00641D","url":null,"abstract":"<p >Hierarchical porous metals have shown great potential in applications such as catalysis and energy storage. However, the dealloying process often causes significant issues such as substantial volume shrinkage and stress corrosion cracking. This is particularly severe for thin strip-shaped hierarchical porous metals, which have poor macroscopic mechanical properties, limiting the application range and prospects of these materials. Therefore, transforming the precursor alloy from a thin strip to a bulk form is a key issue in improving the mechanical properties of hierarchical porous metals. In this study, we successfully prepared bulk three-level hierarchical porous silver (THPS), consisting of micron-sized pores (376 ± 86 μm), submicron pores (280 ± 50 nm), and nanopores (45 ± 20 nm) by combining GASAR technology with the dealloying method. Compression tests show that the mechanical properties of THPS are somewhat reduced compared to the sample before dealloying, but it still demonstrates considerable mechanical properties on a macroscopic scale (elastic modulus of 0.93 GPa and compressive strength of 107.87 MPa). Nanoindentation tests were conducted to analyze the effect of ligament size on mechanical properties. The results indicate that the mechanical properties of THPS decrease as the ligament size increases. Compared to other hierarchical porous silver materials, THPS exhibits better mechanical properties. Experimental results demonstrate that the combined method of GASAR and dealloying can enhance the mechanical properties of hierarchical porous metals, providing new ideas and methods for improving the performance of these materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6127-6136"},"PeriodicalIF":2.6,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intramolecular hydrogen bonding in 1,8-bis(dimethylamino)naphthalenes containing two to four heteroatomic functions in the ortho- and peri-positions: from CD3 to sulfur and selenium","authors":"Valery A. Ozeryanskii, Oleg P. Demidov and Andrey V. Marchenko","doi":"10.1039/D5CE00621J","DOIUrl":"https://doi.org/10.1039/D5CE00621J","url":null,"abstract":"<p >Using 4,5-dibromo- and 2,7-dibromo-4,5-dimethyl-derivatives of 1,8-bis(dimethylamino)naphthalene (naphthalene “proton sponge”) in bromine-lithium exchange and subsequent reactions with appropriate electrophiles, a set of intriguing new derivatives with such functionalities as Br, Me, SMe, and CD<small>₃</small> in various combinations, including compounds with <em>peri</em>-S–S and Se–Se bridges, were synthesized. The subsequent transformation of neutral polyfunctional proton sponges into monoprotonated cations was investigated both in solution and in crystals to reveal new possible limits of the so-called “buttressing effect”, “clothespin effect” and their combination affecting the length (2.50–2.61 Å), symmetry and dynamics (barrier free or low-barrier proton transfer) of the intramolecular H-bridge. In a series of 2,4,5,7-tetrasubstituted cations with an extremely compressed but still accessible for nucleophilic species hydrogen bond, a weak influence of the counterion (tetrahedral BF<small>₄</small><small>⁻</small>, linear SCN<small>⁻</small>, spherical Br<small>⁻</small>) on the properties of the [NHN]<small>⁺</small> bond in spatially overloaded proton sponges was demonstrated. It seems, in such cations a “micro-buttressing effect” is possible, since the replacement of hydrogen by deuterium in <em>ortho</em>-methyl groups results in a new record of compression of the internitrogen distance till 2.498 Å. The reversible redox behavior of the disulfide bridge in the 4,5-S–S-derivative of 1,8-bis(dimethylamino)naphthalene was also described.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6163-6173"},"PeriodicalIF":2.6,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced hydrogen evolution kinetics via GaN/g-C3N4 heterojunction engineering","authors":"Xiangrong Li, Mengzhou Wu, Yanling Wang, Wentao Qu and Guoqiang Li","doi":"10.1039/D5CE00615E","DOIUrl":"https://doi.org/10.1039/D5CE00615E","url":null,"abstract":"<p >Among various semiconductors evaluated for photoelectrochemical (PEC) water splitting, gallium nitride (GaN) has emerged as a promising photoelectrode material due to its wide, direct bandgap, which allows for more efficient sunlight utilization. To address the issue of severe surface states that hinder its performance, graphitic carbon nitride (g-C<small>₃</small>N<small>₄</small>) was introduced as a passivation layer. The resulting GaN/g-C<small>₃</small>N<small>₄</small> heterojunction demonstrates a significant enhancement in PEC performance compared to pristine GaN nanorods (NRs), including a notable increase in photocurrent density. Importantly, this heterostructure is also capable of driving PEC water splitting under zero external bias, which is primarily attributed to the efficient charge separation and transfer enabled by the Z-scheme mechanism. Overall, this study offers a novel strategy for passivating surface states in nanomaterials and underscores the promising role of g-C<small>₃</small>N<small>₄</small> in PEC water splitting applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 6048-6055"},"PeriodicalIF":2.6,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface sensitive catalytic mechanism of morphology and facet controlled α-MnO2 nanostructures in the decomposition of ammonium perchlorate","authors":"Santra Merin Saju and Anuj A. Vargeese","doi":"10.1039/D5CE00732A","DOIUrl":"https://doi.org/10.1039/D5CE00732A","url":null,"abstract":"<p >The catalytic properties of nanostructured materials are significantly influenced by their specific crystallographic facets. Each facet presents unique atomic configurations and electronic structures, which play a crucial role in bond activation, reactant adsorption, and the stabilization of intermediates. This study investigated the influence of distinct α-MnO<small>₂</small> nanostructures on the thermal decomposition of ammonium perchlorate (AP), an important oxidizer in solid propellants. MnO<small>₂</small> nanorods (1D) and nanocubes (3D) were synthesized and their catalytic activities were assessed. Nanocubes, featuring a microporous structure and predominantly exposing the (211) crystallographic facet, demonstrated enhanced catalytic efficiency in the decomposition of AP compared to nanorods primarily exposing the (310) facet. XPS analysis confirmed the presence of Mn<small>⁴⁺</small>/Mn<small>³⁺</small> redox couples and surface oxygen vacancies, which collectively facilitated electron transfer to the perchlorate anion (ClO<small>₄</small><small>⁻</small>), thereby promoting its reduction and accelerating one of the kinetically competing decomposition reactions. This resulted in a significant enhancement in NO<small>₂</small> evolution relative to N<small>₂</small>O, during the decomposition reaction, suggesting a catalyst induced alteration in the decomposition pathway.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6174-6183"},"PeriodicalIF":2.6,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00732a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient solvent-free mechanochemical synthesis of CALF-20 for carbon dioxide capture","authors":"Natchaya Phongsuk, Chalarat Chaemchamrat, Taya Ko Saothayanun, Nopphon Weeranoppanant and Sareeya Bureekaew","doi":"10.1039/D5CE00632E","DOIUrl":"https://doi.org/10.1039/D5CE00632E","url":null,"abstract":"<p >A solvent-free mechanochemical synthesis of CALF-20 is proposed, offering a rapid and cost-effective route by eliminating the solvent used and the purification process. With a record space–time yield of up to 88 000 kg m<small>⁻³</small> d<small>⁻¹</small>, the mechano-synthesized CALF-20 exhibits a high CO<small>₂</small> adsorption capacity, highlighting its potential for point-of-use carbon capture.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 5959-5964"},"PeriodicalIF":2.6,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of spherical and heterogeneous core–shell structure Co@Fe particles and electromagnetic absorption performance investigation","authors":"Hong Li, Hongyang Li, Ningliang Kong, Ruiling Xie, Shentao Zeng, Wenqi Xu, Ran Wang, Cui Luo and Ying Liu","doi":"10.1039/D5CE00472A","DOIUrl":"https://doi.org/10.1039/D5CE00472A","url":null,"abstract":"<p >Chemical liquid-phase coating was used to prepare spherical, flower-shaped, and thorny-shaped Co@Fe composite particles with varying mass ratios of Co : Fe. The effects of reaction conditions on the microstructure, morphology, static magnetic properties and electromagnetic wave absorption characteristics were investigated. The Co@Fe composite particles are primarily composed of Co and Fe, maintaining the morphological features of the original Co particles while exhibiting changes in particle size and surface structure. The average particle diameters of spherical Co@Fe particles were measured to be 1.32 μm, 1.59 μm, and 1.62 μm, with the particle surfaces being relatively smooth when the Co : Fe mass ratio was 1 : 1. For flower-shaped Co@Fe particles, the sizes were 1.59 μm, 1.61 μm, and 2.96 μm, with the original sharp, flake-like petals transforming into rounded, globular protrusions. The average diameters of thorny-shaped Co@Fe particles were approximately 6.11 μm, 7.53 μm, and 8.03 μm, where the spear tips became less sharp and the aspect ratio of the spear-like structure increased. The XRD patterns revealed FCC-Co, HCP-Co, and Fe, and as the Fe content in the Co@Fe particles increased, both saturation magnetization and coercivity decreased. The thorny-shaped Co@Fe particle sample achieved the minimum reflection loss of −16.47 dB at a thickness of 1.8 mm, with an effective absorption bandwidth of 4.96 GHz.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 6030-6047"},"PeriodicalIF":2.6,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemistry-induced deposition for controlled formation of metal–organic framework films on insulator and conductor substrates","authors":"Takashi Ito and Elise A. Skinner","doi":"10.1039/D5CE00727E","DOIUrl":"https://doi.org/10.1039/D5CE00727E","url":null,"abstract":"<p >A number of technological applications of metal–organic frameworks (MOFs) require the formation of their thin films on insulator and/or conductor substrates at selected areas with desired thicknesses. However, fabrication of such MOF films often requires multi-step processes and/or sophisticated instruments. Herein, we discuss electrochemistry-induced MOF deposition, which permits the direct formation of a thin MOF film with controlled thickness at a desired area on various substrates. So far, we have reported the applicability of this deposition method for the formation of zeolitic imidazolate framework-8 (ZIF-8) films. In this method, a ZIF-8 film is formed on an insulator or a conductor substrate upon applying a cathodic potential to a working electrode that is placed above the substrate. Importantly, the film is formed just below the cathodic working electrode, indicating that the position and lateral dimensions (on the mm- to μm-scale) of the film can be controlled by those of the working electrode. In addition, film thickness is controllable in the range of tens to hundreds of nanometers by adjusting potential application conditions at the cathodic working electrode. These results show that the electrochemistry-induced deposition method will provide a simple means for the fabrication of a patterned MOF film on various substrates without additional lithographic processes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6274-6282"},"PeriodicalIF":2.6,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00727e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}