Crystal Growth & Design最新文献

{"title":"High-Quality, Low-Cost Quasi-Bulk Hexagonal Boron Nitride Crystals by LP-HVPE: Machine Learning-Assisted Process Optimization via XRD and Raman Characterization","authors":"Xi Chen,&nbsp;Ziting Han,&nbsp;Weibo Xu,&nbsp;Yalei Zhou,&nbsp;Xiaohang Liu,&nbsp;Lixin Hou,&nbsp;Yanjun Gao,&nbsp;Zhanguo Chen","doi":"10.1021/acs.cgd.6c00635","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00635","url":null,"abstract":"<p>Highly ordered, quasi-bulk hexagonal boron nitride (hBN) films were grown on <em>c</em>-plane sapphire (α-Al₂O₃) substrates via low-pressure hydride vapor-phase epitaxy (LP-HVPE), using industrial-grade boron trichloride (BCl₃) and ammonia (NH₃) as low-cost boron and nitrogen sources, respectively. The effects of four key growth parameters (growth temperature, III/V source flow ratio, growth ambient, and growth pressure) on the crystalline quality of hBN films were systematically investigated via the single-variable method. A gradient boosting regression machine learning (ML) model was constructed based on 24 groups of experimental datasets to achieve high-precision prediction of hBN crystalline quality, with determination coefficients (<em>R</em>²) of 0.96 and 0.94 for the prediction of X-ray diffraction and Raman characteristic peak full width at half maximum, respectively. The optimized growth condition was determined as follows: a growth temperature of 1350 °C, a III/V ratio of 1:3, N₂ ambient, and a growth pressure of 100 Pa, which is consistent with the global optimal parameters obtained by Bayesian optimization combined with the ML model. This work provides a low-cost, high-efficiency route for the controllable preparation of high-quality quasi-bulk hBN crystals via LP-HVPE with ML-assisted optimization.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8713–8721"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"From Structurally Related Solvates to Divergent Anhydrous Polymorphs: Desolvation Pathways of Sotorasib","authors":"Ruoxi Huang,&nbsp;Yue Xu,&nbsp;Jia Tong,&nbsp;Jie Lu","doi":"10.1021/acs.cgd.6c01241","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01241","url":null,"abstract":"<p>Sotorasib is a covalent KRAS G12C inhibitor with multiple hydrogen-bonding sites and conformationally flexible groups, making it prone to solvate formation. In this work, eight sotorasib solvates were obtained and systematically characterized, and their crystal structures were determined by SCXRD. Among them, S_MeOHα, S_DCE, and S_MIX are previously unreported solvates. Except for S_MIX, the other seven solvates crystallize in the same orthorhombic space group with similar unit-cell parameters and a conserved host−host hydrogen-bonding motif, while differences in guest stoichiometry, local interactions, and lattice occupancy generate distinct packing environments. Upon guest removal, these related solvates exhibit divergent post-desolvation evolution, with lattice destabilization followed by thermal-history-dependent structural reorganization toward different anhydrous polymorphs. Under dynamic heating, DSC reveals Form II-related thermal evolution for S_ACN and S_MeOHα, while HSM further identifies melt-mediated recrystallization for S_MeOHα. Molecular dynamics simulations and solvent-vapor-induced transformation experiments further indicate lattice adaptability during guest removal and exchange. These results highlight the roles of lattice environment and thermal history in regulating post-desolvation evolution and polymorph formation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"9049–9061"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intrinsic Fracture Planes of Sapphire","authors":"Fenfen Ding,&nbsp;Lijun He,&nbsp;Binghui Yu,&nbsp;Zhenyu Shi,&nbsp;Sen Kang,&nbsp;Yarong Lu,&nbsp;Jiabao Cheng,&nbsp;Degui Liu,&nbsp;Wei Ma","doi":"10.1021/acs.cgd.6c00399","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00399","url":null,"abstract":"<p>The study of fracture characteristics in sapphire crystals (α-Al₂O₃) is both fascinating and crucial for understanding the failure behavior of this material in relevant applications. However, current conclusions regarding the slip and fracture features of sapphire remain fragmented and unsystematic, particularly concerning the latter. A simple and effective method applicable to structurally similar crystals was proposed in this research: utilizing spatial geometry theory to reconstruct the spatial positions of cleavage planes within crystals through nanoindentation and scanning electron microscopy data. By applying this geometric analysis method to the nanoindentation test results of five typical crystal planes (C, A, M, R, N), information regarding the locations of sapphire’s intrinsic fracture planes and slip planes at room temperature was systematically obtained: (1) within a single unit cell, all six pyramidal planes are cleavage planes: (112̅4), (112̅6), (112̅12), (11̅02), (11̅03), and (11̅06); (2) the C-plane appears to act as the sole slip plane induced by nanoindentation testing at room temperature; no cleavage behavior was observed on this plane.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8654–8667"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Highly Efficient Ternary Composite Sensor with a Thiacalix[4]arene-Based Metal−Organic Framework, Spherical Graphite, and Multi-Walled Carbon Nanotubes for Enhanced Electrochemical Sensing of Rutin","authors":"Yu-Jie Yang,&nbsp;Shuaitong Zhang,&nbsp;Li-Xian Xia,&nbsp;Jian-Fang Ma","doi":"10.1021/acs.cgd.6c00560","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00560","url":null,"abstract":"<p>Rutin, as a natural flavonoid, has been used in various medical treatments. Nevertheless, excessive intake of rutin has certain adverse side effects. Thus, it is essential to develop an efficient and accurate method for detecting rutin. In this work, a new metal−organic framework (MOF), namely, [Cd₂(L)(BDC)₂]·DMF·MeOH (<strong>CdLBDC</strong>), was prepared with a thiacalix[4]arene-based ligand (L), Cd(II) cations, and 1,3-benzenedicarboxylic acid (H₂BDC). Subsequently, spherical graphite (SG), multi-walled carbon nanotubes (MWCNTs), and <strong>CdLBDC</strong> were ground to yield a family of three-component <strong>CdLBDC@MWCNT@SG</strong> composites. Under the optimal test conditions, <strong>CdLBDC@MWCNT@SG(1:1:1)/GCE</strong> exhibited highly sensitive detection of rutin with a low detection limit (0.62 nM). Moreover, <strong>CdLBDC@MWCNT@SG(1:1:1)/GCE</strong> showed acceptable repeatability, stability, and anti-interference ability during the sensing process of rutin. Remarkably, it was used to determine the rutin content in the actual rutin tablet sample with satisfactory recoveries. Obviously, the synergistic effects between the composites effectively facilitated the electrochemical sensing of rutin. This work manifested that the fabrication of the ternary composite sensors was an effective way to improve the electrochemical detection performances.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8691–8699"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chameleonic π-Hole Behavior in Metal−Isocyanide Complexes: N ↔ C Composition-Controlled Migration","authors":"Mikhail A. Kinzhalov,&nbsp;Polina V. Komova,&nbsp;Rosa M. Gomila,&nbsp;Antonio Frontera,&nbsp;Vadim Yu Kukushkin,&nbsp;Nadezhda A. Bokach","doi":"10.1021/acs.cgd.6c01209","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01209","url":null,"abstract":"<p>Cocrystal architecture reflects the cumulative outcome of competing and cooperating noncovalent interactions (NCIs) within the lattice. Here we demonstrate that the electrophilic π-hole of a coordinated aryl isocyanide is chameleonic: its localization migrates between the nitrogen and carbon termini of the C≡N bond in direct response to crystal composition. X-ray diffraction analysis of <em>trans</em>-[PdI₂(CNC₆H₄Cl-4)₂] (<strong>1</strong>) and its iodine cocrystals <strong>1</strong>·I₂ and <strong>1</strong>·2I₂, complemented by the isostructural platinum(II) analogue <strong>2</strong>·I₂, reveals three distinct binding regimes: Pd-π_Ar assembly in the parent complex, Pd-π-(C<span>N</span>) assembly at 1:1 stoichiometry, and π-(<span>C</span>N)-hole···I(LP) contacts at 1:2 stoichiometry. Quantum chemical analysis (Molecular Electrostatic Potential, Quantum Theory of Atoms in Molecules, NCIplot, Energy Decomposition Analysis, Natural Bond Orbital) establishes that the short C≡N bond and the small electrostatic differential between the two termini generate a delocalized π-hole that adapts to spatial demands imposed by competing halogen bonds. Energy decomposition further reveals that the N ↔ C migration is accompanied by a fundamental change in the stabilizing forces, from dispersion- and correlation-dominated stacking to orbital- and electrostatic-driven halogen bonding. These findings establish stoichiometry-controlled π-hole directionality as a design principle for engineering cocrystals in which multiple NCI types coexist in spatially optimized arrangements.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"9008–9022"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stereoregular Cyclosiloxane-Based Tetracarboxylic Acid as a Flexible Building Block for HOF and CP/MOF Design","authors":"Sergey P. Kutumov,&nbsp;Alexander D. Volodin,&nbsp;Alexander A. Korlyukov,&nbsp;Ilia A. Pankin,&nbsp;Alexander A. Guda,&nbsp;Dmitry A. Khanin,&nbsp;Pavel V. Dorovatovskii,&nbsp;Ashot V. Arzumanyan","doi":"10.1021/acs.cgd.6c01095","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01095","url":null,"abstract":"<p>The stereoregular organosilicon ligand, all-<em>trans</em>-tetra(<em>p</em>-carboxyphenyl)-cyclotetrasiloxane (<strong>H</strong>_{<strong>4</strong>}<strong>A</strong>), was utilized as a novel building block for the construction of the HOF and coordination polymers (CPs/MOFs). Strong hydrogen bonding and dense 3-fold interpenetration in the <strong>H</strong>_{<strong>4</strong>}<strong>A-HOF</strong> determined the high thermal and solvolytic stability of <strong>H</strong>_{<strong>4</strong>}<strong>A</strong>. <strong>H</strong>_{<strong>4</strong>}<strong>A</strong> and M(II) form novel crystalline CPs/MOFs in pyridine-containing media under ambient (in Pyr/H₂O, <strong>B−F</strong>) and solvothermal (in Pyr/DMF, <strong>G</strong>) conditions. Pyridine plays a crucial role in the formation and stabilization of <strong>B−G</strong>, facilitating the dissolution of <strong>H</strong>_{<strong>4</strong>}<strong>A</strong> and shaping the coordination environment of M(II). Cd(II)- (<strong>B</strong>), Zn(II)/Cd(II)- (<strong>C</strong>), and Co(II)-based (<strong>D</strong>) products are structurally similar 1D CPs/MOFs of the <strong>2,4C4</strong> topology. Hg(II)- (<strong>F</strong>) and Cd(II)-based (<strong>G</strong>) products are structurally similar 2D CPs/MOFs of the <strong>sql</strong> topology. The influence of solvent inclusion and hydrogen bonding on the CP/MOF aperture size was shown using the example of <strong>B−D</strong>. The influence of the initial reagent phase distribution and mixing order was demonstrated by the growth of 1D and 2D Co(II)-based CPs/MOFs <strong>D</strong> and <strong>E</strong> (<strong>hcb</strong> topology). If the dissolution of <strong>H</strong>_{<strong>4</strong>}<strong>A</strong> is hindered, the templated formation of <strong>E</strong> with an inherited large aperture organization (∼52 × 18 Å) occurs. Structural analysis confirms the flexible nature of the ligand and similar organization patterns of the crystals, thus highlighting the usability of <strong>H</strong>_{<strong>4</strong>}<strong>A</strong> for the CP/MOF design and the preparation of functional materials in the future.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8947–8965"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308273","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of Homochiral Complexes Based on Imidazole-Decorated Salen-Type Schiff Bases: Photochromism and Enantiomer Recognition of Penicillamine","authors":"Mao-Juan Tian,&nbsp;Chao Huang,&nbsp;Bi-Xue Zhu,&nbsp;Chun Zhu","doi":"10.1021/acs.cgd.6c00646","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00646","url":null,"abstract":"<p>Two imidazole-decorated salen-type Schiff base ligands (H₂<strong>L</strong>_{<strong><em>R</em></strong>} and H₂<strong>L</strong>_{<strong><em>S</em></strong>}) were synthesized and characterized. Five pairs of homochiral complexes, namely, {[Cd(H₂<strong>L</strong>_{<strong><em>R</em></strong>})Cl₂]·DMF}_<em>n</em> (<strong>1a</strong>), {[Cd(H₂<strong>L</strong>_{<strong><em>S</em></strong>})Cl₂]·DMF}_<em>n</em> (<strong>1b</strong>), {[Cd(H₂<strong>L</strong>_{<strong><em>R</em></strong>})Br₂]·DMF}_<em>n</em> (<strong>2a</strong>), {[Cd(H₂<strong>L</strong>_{<strong><em>S</em></strong>})Br₂]·DMF}_<em>n</em> (<strong>2b</strong>), {[Cd(H₂<strong>L</strong>_{<strong><em>R</em></strong>})I₂]·2DMF·H₂O}_<em>n</em> (<strong>3a</strong>), {[Cd(H₂<strong>L</strong>_{<strong><em>S</em></strong>})I₂]·2DMF·H₂O}_<em>n</em> (<strong>3b</strong>), {[Cu₂(<strong>L</strong>_{<strong><em>R</em></strong>}²⁻)Cl₂]·DMF·MeCN}_<em>n</em> (<strong>4a</strong>), {[Cu₂(<strong>L</strong>_{<strong><em>S</em></strong>}²⁻)Cl₂]·DMF·MeCN}_<em>n</em> (<strong>4b</strong>), [Ni(<strong>L</strong>_{<strong><em>R</em></strong>}²⁻)]·DMF·2H₂O (<strong>5a</strong>), and [Ni(<strong>L</strong>_{<strong><em>S</em></strong>}²⁻)]·DMF·2H₂O (<strong>5b</strong>), were synthesized by reacting the two ligands with Cd(II), Cu(II), and Ni(II) ions, respectively. Crystal structures of these complexes revealed three different coordination modes of the ligands, resulting in the formation of microparticles with different morphologies in methanol. The photochromic properties of the ligands and complexes were examined and the results revealed that the ligands and the three pairs of Cd(II) complexes, especially <strong>2a</strong>/<strong>2b</strong>, exhibited photochromism originating from enol−keto tautomerism followed by <em>cis</em>−<em>trans</em> isomerization of the salicylaldehyde imine units. Circular dichroism spectra and density functional theory calculations revealed that <strong>5a</strong>/<strong>5b</strong> exhibited obvious enantiomer recognition of <em>D</em>-/<em>L</em>-penicillamine (<strong><em>D</em>-</strong>/<strong><em>L</em>-Pen</strong>) in their host−guest binding interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8722–8736"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluoride Substitution Changes Vanadium Valence from Nonmagnetic V5+ to Magnetic V4+ in Kagomé Lattice KV3(SeO3)2O3F3","authors":"Tianyu Zhu,&nbsp;Zhiying Zhao,&nbsp;Meiyan Cui,&nbsp;Wenhao Zhang,&nbsp;Zhangzhen He","doi":"10.1021/acs.cgd.6c00954","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00954","url":null,"abstract":"<p>Kagomé compounds have attracted great interest in materials science and condensed matter physics owing to their unique structures and rich exotic magnetic phenomena. In this work, starting from the nonmagnetic kagomé lattice compound KV⁵⁺₃(SeO₃)₂O₆, we successfully obtained a new kagomé compound KV₃(SeO₃)₂O₃F₃ by introducing F⁻ ions to tune the valence state of vanadium. This compound crystallizes in the trigonal space group <em>R</em>-3<em>m</em>, featuring a regular <em>S</em> = 1/2 kagomé layer composed of V⁴⁺ ions. Magnetic and heat capacity measurements reveal a long-range ferromagnetic order below ∼3.1 K.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8867–8872"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First Bulk AlGaN Crystals Grown by the Basic Ammonothermal Method","authors":"Robert Kucharski,&nbsp;Karolina Grabianska,&nbsp;Magdalena A. Zajac,&nbsp;Petro Sadovyi,&nbsp;Patrik Straňák,&nbsp;Lutz Kirste,&nbsp;Marouane Ammar,&nbsp;Nevine Rochat,&nbsp;Łukasz Borowik,&nbsp;Michal Bockowski,&nbsp;Tomasz Sochacki","doi":"10.1021/acs.cgd.6c00597","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00597","url":null,"abstract":"<p>Bulk aluminum−gallium nitride (Al_<em>x</em>Ga_{1−<em>x</em>}N) crystals were synthesized by the basic ammonothermal method using native ammonothermal GaN (Am-GaN) seeds to investigate the influence of growth geometry on structural quality. Conventional growth predominantly along the polar direction produced continuous but highly mosaic Al_<em>x</em>Ga_{1−<em>x</em>}N bulk layers with numerous low-angle grain boundaries and a high dislocation density. A modified configuration promoting lateral growth produced distinct growth sectors with markedly different defect structures. One laterally grown sector exhibited homogeneous X-ray topography contrast, no observable etch pits within the investigated area, and anomalous X-ray transmission associated with the Borrmann effect. Energy-dispersive X-ray spectroscopy showed an Al content of approximately 6 at. % (<em>x</em> ≈ 0.06) across the investigated lateral and polar sectors within the accuracy of the method. The results demonstrate that local growth geometry strongly affects strain accommodation and defect evolution during ammonothermal Al_<em>x</em>Ga_{1−<em>x</em>}N growth. High-quality lateral sectors may provide suitable seed material for subsequent regrowth toward larger, low-defect Al_<em>x</em>Ga_{1−<em>x</em>}N crystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8700–8712"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Naphthalenedisulfonic Acid-Regulated Ionic HOFs Enabling Single-Crystal Superprotonic Conductivity","authors":"Xiao-Ying Hou,&nbsp;Xiao-Jie Cao,&nbsp;Xu-Yong Chen,&nbsp;Wenmin Zhang,&nbsp;Li-Hui Cao","doi":"10.1021/acs.cgd.6c00758","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00758","url":null,"abstract":"<p>Designing ionic hydrogen-bonded organic frameworks (iHOFs) with single-crystal superprotonic conductivity is of great significance for unraveling the mechanisms of proton-conductive materials at the molecular level. To regulate proton transport pathways, we synthesized two novel ionic hydrogen-bonded organic frameworks, <strong>iHOF-60</strong> and <strong>iHOF-61</strong>, by adjusting the spatial configuration of the sulfonate groups. Both materials exhibit three-dimensional hydrogen-bonding networks and highly anisotropic proton conductivity, and clear proton transport pathways were identified through single-crystal structure analysis. Notably, experimental results show that <strong>iHOF-60</strong> achieves a proton conductivity of up to 0.216 S cm⁻¹ along the <em>a</em>-axis at 80 °C and 85% relative humidity, demonstrating exceptional superprotonic conduction performance. Density functional theory (DFT) calculations further confirm that <strong>iHOF-60</strong> possesses superior proton transport properties compared to <strong>iHOF-61</strong>, which is attributable to its more continuous hydrogen-bonding network, smoother proton-transport pathway, and lower steric hindrance. These findings provide new experimental and theoretical insights for the design of high-performance proton-conducting materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8753–8758"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}