CrystEngComm最新文献

{"title":"Formation of “hair” inclusions and growth optimization for large aperture KDP crystals based on the numerical simulation method","authors":"Jianyu Bai, Shumo Zhou, Baoan Liu, Mingxia Xu, Jianfeng Zhang, Lisong Zhang, Hongkai Ren, Shenglai Wang, Xinguang Xu and Xun Sun","doi":"10.1039/D6CE00144K","DOIUrl":"https://doi.org/10.1039/D6CE00144K","url":null,"abstract":"<p >“Hair” inclusion defects in large-aperture KDP/DKDP crystals degrade the performance of high-power laser systems because they adversely modulate the laser beam. This study investigates the formation mechanism of these defects and optimizes the growth parameters through numerical simulation of the solution circulating growth system. A self-consistent crystal growth rate model coupling fluid dynamics, heat transfer, and solute transport is developed. The results reveal that crystal rotation-induced centrifugal flow generates vortex structures, forming localized low-supersaturation regions near the pyramidal face edges. Subsequently, growth step aggregation and mother liquor entrapment may promote the formation of “hair” inclusion. In addition, orthogonal experiments quantified the impact of growth parameters, showing that the inlet temperature differential predominantly governs surface thermal uniformity, while the equilibrium temperature critically influences solute distribution. Further, an optimal parameter combination (inlet temperature differential of 2 °C, inlet flow velocity of 0.36 cm s<small>⁻¹</small>, crystal rotation rate of 8 rpm, and equilibrium temperature of 40 °C) was proposed, which significantly improved thermal uniformity and solute transport on crystal surfaces, thereby being expected to reduce the likelihood of “hair” inclusion formation. An optimization strategy for achieving high-efficiency, low-defect growth of large-aperture KDP-type crystals has been developed, providing important support for the precise control of crystal growth.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3331-3341"},"PeriodicalIF":2.6,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148141607","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":"Effect of different defect dipoles on the polarization mechanism of Nb-doped SrTiO3 single crystals","authors":"Lei Wang, Jiapeng Wang, Yilin Wu, Jianyi Ma, Jinsheng Li, Xiaoguo Bi, Xudong Sun and Weiping Lu","doi":"10.1039/D5CE01210D","DOIUrl":"https://doi.org/10.1039/D5CE01210D","url":null,"abstract":"<p >Although widely recognized for its potential to deliver a colossal permittivity, the origins of this extraordinary property in SrTiO<small>₃</small> are still not fully clarified, necessitating further investigation. In this work, Nb-doped SrTiO<small>₃</small> single crystals were prepared by the Verneuil method, and the influence of different defect dipoles on their dielectric properties was systematically investigated. The study revealed that oxygen-vacancy-associated defect dipoles <img> and <img> are effective in localizing free electrons. Under these conditions, electronic polarization mediated by defect dipoles is present in all samples, contributing to a high permittivity while maintaining low loss. The concentration of these defect dipoles, and thus the dielectric performance, can be effectively tuned by varying the doping level and annealing atmosphere. Notably, defect dipoles <img> capable of efficiently trapping free electrons lead to superior properties. Ultimately, the SrNb<small>_0.5%</small>Ti<small>_99.5%</small>O<small>₃</small> crystal annealed in an oxygen atmosphere tends to form more defect dipoles <img>, yielding a permittivity of 63 217 and a loss tangent of 0.0208 at 1 kHz. This work provides crucial guidance for designing high-performance SrTiO<small>₃</small>-based dielectric materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3342-3352"},"PeriodicalIF":2.6,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148141608","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":"Metal-ion-dependent polarity switching and dielectric enhancement in solvent-vapour-responsive mononuclear complexes","authors":"Fumiya Kobayashi, Hiroki Iwase, Shoma Hoshino and Makoto Tadokoro","doi":"10.1039/D5CE01141H","DOIUrl":"https://doi.org/10.1039/D5CE01141H","url":null,"abstract":"<p >Design of molecular materials that exhibit multiple cooperative responses to external stimuli is a key challenge in the development of next-generation functional materials. Herein, we report solvent-vapour-responsive mononuclear Fe(<small>III</small>) and Mn(<small>III</small>) complexes, [M(azdp)(acac)(sol)] (M = Fe, Mn; H<small>₂</small>azdp = 2,2′-azodiphenol; sol = MeOH, DMSO), which undergo solvent-vapour-driven structural transformations between polar and nonpolar molecular assemblies through ligand exchange at the solvent coordination site. The Fe(<small>III</small>) complexes exhibited pronounced cooperative aggregation upon DMSO coordination, generating polar molecular packings that showed strong second harmonic generation (SHG), enhanced dielectric constants, and ferroelectric-like relaxor behaviour. By contrast, the Mn(<small>III</small>) analogues form centrosymmetric dimers stabilised by Jahn–Teller distortion, resulting in nonpolar assemblies and SHG inactivity. These findings revealed a direct relationship between the metal-centred electronic structure, ligand geometry, and aggregation-induced functionality. The cooperative transformations integrate optical and dielectric functionalities within a single molecular platform, demonstrating a generalisable strategy for constructing solvent-vapour-responsive polar coordination materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 22","pages":" 3499-3505"},"PeriodicalIF":2.6,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ce/d5ce01141h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148193722","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":"Directionality in cation–anion interactions involving chalconium cations","authors":"Mariusz Michalczyk, Steve Scheiner and Wiktor Zierkiewicz","doi":"10.1039/D6CE00102E","DOIUrl":"https://doi.org/10.1039/D6CE00102E","url":null,"abstract":"<p >The directionality of bonds is an important feature for many compounds relevant in biochemistry, crystal engineering and materials chemistry. It is widely accepted that a good number of contacts between ions (including ionic bonds) are nondirectional. A CSD survey is employed to demonstrate that significant directionality of cation⋯anion interactions is observed for systems which include a chalconium cation. Nearly 70% of all found structures contain a R–Y⋯LB angle (Y = S, Se, Te; LB = atom from anionic Lewis base) within 10° of linearity. Such structural motifs are commonly termed charge-assisted chalcogen bonds. Quantum chemical analysis traces this angular tendency to a compromise between coulombic forces and exchange repulsion, which pull in opposite directions. Charge transfer, polarization, and dispersion terms are much smaller in magnitude and thus exert a lesser influence.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3396-3404"},"PeriodicalIF":2.6,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ce/d6ce00102e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148141613","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":"Formation pathways and structural diversity of colloidal tetramers in a two-dimensional system: a Brownian dynamics study","authors":"Masahide Sato, Hiroyasu Katsuno and Yoshihisa Suzuki","doi":"10.1039/D6CE00204H","DOIUrl":"https://doi.org/10.1039/D6CE00204H","url":null,"abstract":"<p >The formation of colloidal crystals provides a valuable model system for understanding crystallization mechanisms, because their slow dynamics and large length scales allow direct observation of nucleation and growth processes. In our previous studies, we found that small clusters often adopt non-compact shapes, in contrast to the classical nucleation theory assumption that clusters remain compact during growth. Nevertheless, their size distribution is essentially the same as that of compact clusters. In this work, we perform Brownian dynamics simulations in four-particle systems to investigate the shape transitions of tetramers, the smallest clusters capable of exhibiting multiple geometries. Our results show that clusters do not adopt the most compact shapes under near-equilibrium conditions, particularly at low supersaturation. We also reveal in detail the process by which tetramers change their own shape.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 22","pages":" 3466-3474"},"PeriodicalIF":2.6,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148193719","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":"Layered indium–silver-based hybrid perovskite single crystals for high-performance X-ray detection","authors":"Luying Zheng, Binyan Qiu, Xin Huang, Yi Zheng, Min Chen, Xiaoming Jiang, Xieming Xu, Shaofan Wu and Shuaihua Wang","doi":"10.1039/D6CE00095A","DOIUrl":"https://doi.org/10.1039/D6CE00095A","url":null,"abstract":"<p >To overcome the lead toxicity and ion migration drawbacks of hybrid perovskites in X-ray detection, a two-dimensional indium–silver-based hybrid perovskite, BDA<small>₂</small>AgInBr<small>₈</small> with a Dion–Jacobson-type layered structure, is yielded through a dual design strategy combining Ag<small>⁺</small>/In<small>³⁺</small> substitution with the introduction of the 1,4-butanediamine cation. The well-balanced interlayer spacing of 4.23 Å enhances both charge transport and environmental stability. BDA<small>₂</small>AgInBr<small>₈</small> single-crystal detectors show a low detection limit of 120 nGy<small>_air</small> s<small>⁻¹</small>, a high sensitivity of 1565 μC Gy<small>_air</small><small>⁻¹</small> cm<small>⁻²</small> and a radiation hardness up to 51.2 Gy<small>_air</small>. This result confirms that cation replacement and layered structure regulation are an effective route to high-performance, stable and eco-friendly X-ray detection materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3267-3273"},"PeriodicalIF":2.6,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011692","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":"Dative and noncovalent tetrel bonding in hemidirected Pb(ii) complexes with thiosemicarbazone and hydrazone ligands: significance in crystal packing and computational insights into Pb⋯N/S/O interactions","authors":"Suman Adhikari, Sourav Nath, Werner Kaminsky, Sebastian Krajewski, Rahul Shukla and Subhadip Roy","doi":"10.1039/D6CE00202A","DOIUrl":"https://doi.org/10.1039/D6CE00202A","url":null,"abstract":"<p >Supramolecular architectures in lead(<small>II</small>) coordination compounds are increasingly recognized for their reliance on unconventional noncovalent interactions, particularly tetrel bonding involving the heavy tetrel atom Pb(<small>II</small>). In this work, two new Pb(<small>II</small>) complexes, [Pb(HL<small>¹</small>)(H<small>₂</small>L<small>¹</small>)]ClO<small>₄</small> (<strong>1</strong>) and [Pb<small>₂</small>(L<small>²</small>)<small>₂</small>]·2H<small>₂</small>O·DMSO (<strong>2</strong>) were synthesised using thiosemicarbazone-based and hydrazone-based Schiff base ligands (H<small>₂</small>L<small>¹</small> and H<small>₂</small>L<small>²</small>, respectively). Both complexes were characterized by elemental analysis, FT-IR, <small>¹</small>H NMR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that complex <strong>1</strong> contains a [Pb(HL<small>¹</small>)(H<small>₂</small>L<small>¹</small>)]<small>⁺</small> cationic moiety in which the Pb(<small>II</small>) centre is coordinated by one deprotonated anionic ligand (HL<small>¹</small>)<small>⁻</small> in a bidentate N,S fashion and one neutral ligand (H<small>₂</small>L<small>¹</small>) in a monodentate S fashion, charge-balanced by a perchlorate anion. In contrast, complex <strong>2</strong> contains two crystallographically independent Pb(<small>II</small>) centres (Pb1 and Pb2) coordinated by the doubly deprotonated ligand (L<small>²</small>)<small>²⁻</small> in a tridentate ONO fashion with pyridine nitrogen bridging, affording discrete dinuclear Pb<small>₂</small> units. Both complexes exhibit hemidirected coordination geometries around the Pb(<small>II</small>) centers, which facilitate the formation of dative coordinate bonds (Pb←N) and noncovalent tetrel bonding interactions (Pb⋯S/Pb⋯O), alongside conventional hydrogen bonds (C–H⋯O/S and N–H⋯O/N). These interactions drive the assembly of three-dimensional supramolecular frameworks. Electrostatic potential maps confirm the σ-hole character at the Pb(<small>II</small>) centers, while computational calculations (M06-2X/def2-TZVP) and QTAIM analysis quantify the strength and the electron-density topology of these interactions. This study highlights the pivotal role of Pb(<small>II</small>)-centered tetrel bonding in directing the supramolecular organization of Pb(<small>II</small>) complexes, offering valuable insights for crystal engineering and the design of functional materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 23","pages":" 3579-3588"},"PeriodicalIF":2.6,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148247647","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":"Multi-stimuli chromic responses (light/electro/amino-) in Zn/Cd-extended viologen materials toward information encryption","authors":"Chen-Ran Zhang, Ming Xiao, Qun-Shan Ding, Lin-Ke Li, Xue-Li Zhao and Shuang-Quan Zang","doi":"10.1039/D6CE00124F","DOIUrl":"https://doi.org/10.1039/D6CE00124F","url":null,"abstract":"<p >Significant progress has been made in the research of stimuli-responsive materials in recent years. Among these, viologen-based functional coordination compounds have shown remarkable prominence due to the excellent redox properties of viologens. Herein, a π-conjugation extension strategy was employed by introducing a diphenyl sulfone group between the viologen pyridine units to enhance its performance. Using this extended viologen 4,4′-(sulfonylbis(4,1-phenylene))bis(1-(4-carboxybenzyl)pyridin-1-ium) chloride [(H<small>₂</small>L)·2Cl] as a ligand, with d<small>¹⁰</small> configured metals (Zn<small>²⁺</small>/Cd<small>²⁺</small>) as central atoms and terephthalic acid (PTA) as an auxiliary ligand, two novel crystalline materials {[Zn(L)(PTA)(H<small>₂</small>O)]·4H<small>₂</small>O}<small>_<em>n</em></small> (<strong>1</strong>) and {[Cd(L)(PTA)<small>_0.5</small>(FA)]·6H<small>₂</small>O}<small>_<em>n</em></small> (<strong>2</strong>) were successfully constructed. Both materials exhibit rapid and reversible photochromic behavior. The mechanism for this photochromic behavior is attributed to electron transfer from carboxylate groups and water molecules to viologen pyridine nitrogen atoms. Furthermore, the materials possess excellent electrochromic properties, showing good reversibility in air and a specific color change response toward amine vapors. This work aims to develop stimuli-responsive materials that combine structural stability with functional diversity, thereby enriching the range of materials available in this field.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 23","pages":" 3609-3620"},"PeriodicalIF":2.6,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148247650","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":"Complete structural and electronic comparison of chiral and racemic ketohexoses: hydrogen-bond network topology and interaction strength distribution","authors":"Tomoko Takashita, Ryunosuke Takata, Mizuki Aoe, Kei Takeshita and Tomohiko Ishii","doi":"10.1039/D6CE00205F","DOIUrl":"https://doi.org/10.1039/D6CE00205F","url":null,"abstract":"<p >Racemic crystals are generally expected to exhibit higher densities than their enantiopure counterparts owing to complementary packing of enantiomers (Wallach's rule), yet the structural origin of its deviation in hydrogen-bonded systems remains unclear. Here, we present a systematic comparison of four ketohexoses in both chiral and racemic forms, including the first single-crystal structure of racemic <small>D</small>,<small>L</small>-tagatose (<em>P</em>2<small>₁</small>/<em>c</em>), thereby completing the structural series of racemic ketohexoses within this constitutional isomer family. Density analysis shows that fructose and sorbose conform to Wallach's rule, whereas psicose and tagatose form less dense racemic crystals. Interaction-frame analysis reveals that compliance with the rule is associated with compact dimer-dominated networks, while deviations correlate with expanded triangular and square motifs. Bond overlap population (BOP) calculations demonstrate that fructose, psicose, and sorbose possess hierarchically concentrated hydrogen-bond strengths preserved upon racemization, whereas tagatose exhibits a more dispersed interaction pattern. Notably, psicose retains electronic hierarchy despite deviating from Wallach's rule, indicating that electronic strength alone does not determine packing efficiency. Together with FIMs analysis, these findings indicate that deviation from Wallach's rule reflects cooperative coupling between hydrogen-bond topology and electronic interaction hierarchy.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3387-3395"},"PeriodicalIF":2.6,"publicationDate":"2026-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148141612","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":"Subtle symmetry breaking in averievite-related compounds, (MX)Cu5O2(VO4)2 (MX = CsBr, CsI, RbBr, RbI and KI)","authors":"Ilya V. Kornyakov, Olga G. Bubnova, Alexey A. Kalinichev, Marina V. Likholetova and Sergey V. Krivovichev","doi":"10.1039/D5CE00495K","DOIUrl":"https://doi.org/10.1039/D5CE00495K","url":null,"abstract":"<p >In this work, we report a previously unrecognized type of phase transition within the averievite family of compounds, (MX)Cu<small>₅</small>O<small>₂</small>(VO<small>₄</small>)<small>₂</small> (MX = <strong>CsBr</strong>, <strong>CsI</strong>, <strong>RbBr</strong>, <strong>RbI</strong> and <strong>KI</strong>). Using temperature-dependent single-crystal X-ray diffraction analysis we identified a structural transition from the high-symmetry <em>P</em><img><em>m</em>1 aristotype to a superstructure with <em>a</em> = <em>b</em> ≈ <img>, and <em>c</em> = <em>c</em><small>₀</small>. The superlattice reflections were observed in the five studied (MX)Cu<small>₅</small>O<small>₂</small>(VO<small>₄</small>)<small>₂</small> compounds: the Cs-bearing phases undergo the transition at approximately 125 K, the <strong>RbI</strong> compound shows the presence of superlattice reflections at temperatures above 375 K, whereas the <strong>KI</strong> and <strong>RbBr</strong> compounds exhibit persistent superlattice reflections across the entire temperature interval. The transition is accompanied by a pronounced pseudotranslational symmetry, which hinders the choice between nonpolar <em>P</em><img> and polar <em>P</em>31<em>m</em> space groups on the basis of X-ray diffraction alone. Due to the high absorption of the pure-phase <strong>RbBr</strong> sample and instrumental limitations, no second-harmonic generation signal was detected under the present experimental conditions. However, detailed intensity-statistics analysis of the observed reflections, symmetry and crystal–chemical arguments suggest that the polar <em>P</em>31<em>m</em> space group is the most plausible one.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3907-3926"},"PeriodicalIF":2.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336660","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}