ACS Publications最新文献

{"title":"Mixed –N/–O Surface Terminations Enable Fast Ammonium-Ion Storage in Ti3C2Tx MXene","authors":"Xiang Liu,&nbsp;Mutian Zhang,&nbsp;Wei Zheng,&nbsp;Junjiang Fan,&nbsp;Miaoxi Guo,&nbsp;Li Yang,&nbsp;ZhengMing Sun,&nbsp;Guobing Ying","doi":"10.1021/acsami.6c14469","DOIUrl":"10.1021/acsami.6c14469","url":null,"abstract":"<p>Aqueous ammonium-ion batteries are promising for safety, low cost, and fast energy storage. However, the influence of electrode surface chemistry on NH₄⁺ storage remains poorly understood. Two-dimensional Ti₃C₂T_<em>x</em> MXene, with metallic conductivity, tunable interlayer spacing, and abundant surface terminations, serves as an ideal platform to elucidate NH₄⁺ storage mechanisms. Herein, the role of MXene surface termination in regulating NH₄⁺ storage behavior is systematically investigated using density functional theory calculations and experimental validation. The calculations reveal that the –N terminations offer moderate NH₄⁺ adsorption and high electronic conductivity for rapid charge transfer and ion transport, whereas the –O terminations exhibit stronger ion affinity and enhanced surface stability. Importantly, the mixed –N/–O terminations effectively balance adsorption strength and transition-state stabilization, resulting in the lowest NH₄⁺ migration barrier among the modeled pathways. The calculations employ idealized vacuum-separated surfaces with isolated NH₄⁺ and do not explicitly include solvation or electrolyte effects. Guided by these findings, a mixed –N/–O terminated Ti₃C₂T_<em>x</em> MXene is constructed via a urea-assisted hydrothermal strategy. The optimized NTC-20 electrode delivers 107 mAh g^–1 at 1 A g^–1, retains 67% capacity at 10 A g^–1, and maintains 91% capacity after 10,000 cycles. Ex situ XRD, XPS, and FTIR analyses are consistent with reversible NH₄⁺-associated changes in the local chemical environment and possible storage involving Ti–N···H–N and Ti–O···H–N interactions. Furthermore, the NTC-20//MnO₂/CNTs full cell achieves an energy density of 26.7 Wh kg^–1 at 1.3 kW kg^–1. The results support a dominant role for mixed –N/–O terminations in regulating NH₄⁺ adsorption and diffusion, providing insights into surface-termination engineering for high-performance AAIBs.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"18 41","pages":"56169–56181"},"PeriodicalIF":7.8,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Next-Generation Autocatalysis-Integrated Antibody-Bioorthogonal Catalyst Conjugates for Amplified Cell-Surface Antigen Imaging and Targeted In Situ Prodrug Activation","authors":"Xiaotian Tang,&nbsp;Lei Song,&nbsp;Tengfang Li,&nbsp;Chen Gao,&nbsp;Xiaoqiong Yuan,&nbsp;Guhuan Liu,&nbsp;Yu Wang","doi":"10.1021/acsami.6c17507","DOIUrl":"10.1021/acsami.6c17507","url":null,"abstract":"<p>Immunoassays and antibody–drug conjugates (ADCs) rely on specific antigen–antibody recognition for biomarker detection and targeted cancer therapy; however, their practical performance is often hampered by low antigen abundance, which yields weak readout signals or insufficient local drug concentrations. Autocatalytic bioorthogonal reactions offer an attractive route to achieve exponential signal amplification, but existing CuAAC-based autocatalytic systems suffer from slow multistep ligand assembly and fluorophore self-quenching that degrade signal-to-background ratios. Herein, we report a next-generation autocatalysis-integrated bioorthogonal catalyst-linked immunosorbent assay (BCLISA) employing bis(triazolylmethyl)aminopropyne (DTTA) as a key autocatalytic precursor. Unlike the prior tripropargylamine (TPA) system that demands three successive CuAAC events for ligand formation, DTTA assembles active tris(triazolylmethyl)amine ligands via only one single CuAAC reaction with 7-azidocoumarin (7AC), incorporating merely one coumarin moiety per ligand to mitigate fluorescence self-quenching. Benefiting from accelerated kinetics and suppressed self-quenching, DTTA-mediated autocatalysis enables sensitive in vitro detection of recombinant HER2 and BK polyomavirus VP1 antigens, outperforming commercial ELISA kits. Functionalized with <em>n</em>-octyl lipid tails, DTTA-C8 anchors autocatalytic cascades onto living cell membranes, allowing confocal imaging and quantitative measurement of low-abundance cell-surface antigens free from endogenous enzyme interference. Furthermore, autocatalytically generated copper catalytic centers drive local CuAAC-mediated prodrug cyclization to produce cytotoxic agents. Distinct from conventional ADC approaches that pursue high drug-to-antibody ratios, our strategy achieves targeted in situ drug activation without heavy antibody modification, retaining native antibody-binding capacity and eliciting antigen-selective cancer-cell death. This work illustrates the utility of rationally optimized autocatalytic bioorthogonal cascades to couple antibody-based molecular recognition with exponential chemical amplification for both diagnostic and therapeutic applications.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"18 41","pages":"56005–56014"},"PeriodicalIF":7.8,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrasound-Triggered Site-Specific Chemistry Redefines Precision Oncology","authors":"Xinxin Xie,&nbsp;Shuyu Xu,&nbsp;Haonan Wang,&nbsp;Yuxuan Tong,&nbsp;Savas Sonmezoglu,&nbsp;Ozlem Ates Sonmezoglu,&nbsp;Xiaolong Liang","doi":"10.1021/acs.bioconjchem.6c00403","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00403","url":null,"abstract":"<p>Ultrasound-triggered site-specific molecular chemistry has emerged as a transformative strategy for cancer therapy, yet precise spatiotemporal control of their activity remains a critical bottleneck. Endogenous stimulus-responsive strategies are hampered by tumor heterogeneity, while exogenous physical triggers provide superior controllability. This article proposes that ultrasound-triggered site-specific chemistry, termed “acoustic programming”, offers a transformative solution. By integrating focused ultrasound deep-tissue penetration with molecular-level chemical control, acoustically programmable bioconjugates achieve deep-tissue, on-demand therapeutic activation. We survey recent advances in sono-labile linkers, ultrasound-triggered charge reversal, and sono-chemically activated prodrugs, and critically evaluate emerging proof-of-concept and in vivo validated applications in ultrasound-caged PROTACs, immunomodulators, and antibody-drug conjugates. This paradigm shift from “ultrasound-responsive materials” to “ultrasound-responsive molecules” positions acoustic programming as a core platform technology for next-generation precision oncology.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"1935–1942"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221928","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":"Electrostatic Complementarity as a Design Principle for Lamellar Packing in Nitro-Containing CHON Energetic Materials","authors":"Rupeng Bu,&nbsp;Xinlei Jia,&nbsp;Yaoyao Linghu","doi":"10.1021/acs.cgd.6c00723","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00723","url":null,"abstract":"<p>The long-standing trade-off between energy density and mechanical safety has severely restricted the development of advanced energetic materials. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB), the prototypical insensitive high-energy material (IHEM), owes its low sensitivity to a graphite-like lamellar structure, yet no quantitative model currently relates its intermolecular interactions to this lamellar assembly. Herein, we systematically decipher the hierarchical intermolecular interaction network of TATB through a multi-scale theoretical approach. We first identify a bimodal non-uniform interlamellar spacing (3.125 Å and 3.154 Å) in TATB and fully quantify the three-dimensional anisotropy of its intermolecular interactions in type, strength, and directionality. By combining electrostatic potential (ESP) and van der Waals analyses, we first elucidate the electronic origin of this anisotropy. Building on a gradient amino-substituted homologous series and nitro-containing CHON molecules, we further demonstrate that ESP complementarity decisively governs two-dimensional molecular expansion. Finally, we translate these findings into three actionable molecular screening criteria: backbone planarity, alternating donor−acceptor topology, and multidirectional in-plane ESP complementarity. This work provides a quantitative theoretical framework and practical guidance for the rational design of next-generation high-performance insensitive high-energy materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8173–8187"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221915","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":"Towards Phase-Pure Cubic GaN on GaP: Suppression of Hexagonal Inclusions by Low-Temperature Buffer Engineering","authors":"José Santis Espinosa,&nbsp;Yoanlys Hernández Barrios,&nbsp;Ángel Sacramento Orduño,&nbsp;Carlos Marín García,&nbsp;Svetlana Mansurova,&nbsp;José Sánchez López,&nbsp;Salvador Garduño Vértiz","doi":"10.1021/acs.cgd.6c00839","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00839","url":null,"abstract":"<p>Phase-pure cubic GaN (c-GaN) was grown on GaP(001) substrates by low-pressure metal−organic chemical vapor deposition (LP-MOCVD) to evaluate the influence of substrate nitridation and low-temperature GaN buffer layers on phase stability and crystalline quality. Structural and morphological characterization by X-ray diffraction (XRD), Raman spectroscopy, and atomic force microscopy (AFM) showed that the incorporation of a low-temperature buffer layer effectively suppresses hexagonal GaN inclusions and promotes single-phase cubic growth. Raman spectra exhibited the characteristic vibra-tional modes of c-GaN, while XRD analysis revealed narrower c-GaN(200) diffraction peaks, indicating improved crystallinity, larger crystallite size, and reduced defect-related broadening. AFM measurements further demonstrated enhanced grain coalescence and surface uniformity. These findings highlight low-temperature buffer-layer engineering as an effective strategy for stabilizing cubic GaN and improving the structural quality of c-GaN/GaP heterostructures for future electronic and optoelectronic applications.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8232–8242"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221919","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":"Ge Doping in LPCVD-Grown (010) β-Ga2O3 Homoepitaxial Films: Structural, Electrical, and Schottky Diode Characteristics","authors":"Ahmed Ibreljic,&nbsp;Saleh Ahmed Khan,&nbsp;Sourav Sarker,&nbsp;Stephen Margiotta,&nbsp;Stephen Lam,&nbsp;Anhar Bhuiyan","doi":"10.1021/acs.cgd.6c00894","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00894","url":null,"abstract":"<p>Ge-doped β-Ga₂O₃ homoepitaxial films were grown on native (010) β-Ga₂O₃ substrates using low-pressure chemical vapor deposition (LPCVD). Controlled n-type doping was achieved with room-temperature carrier concentrations ranging from 7.4×10¹⁷ to 2.57×10¹⁸ cm⁻³ and corresponding electron mobilities of 105−62 cm²/V·s. The films exhibited smooth surface morphology with RMS roughness values of 2.94−3.97 nm, while X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy confirmed phase-pure β-Ga₂O₃ with excellent crystalline quality and near-stoichiometric composition. Temperature-dependent Hall measurements on the film with a room-temperature carrier concentration of 7.4×10¹⁷ cm⁻³ and mobility of 105 cm²/V·s yielded a peak electron mobility of 234 cm²/V·s at 116 K, while charge-neutrality and transport modeling revealed a dominant shallow donor level with an activation energy of 14 meV, confirming efficient electrical activation of Ge donors. Vertical Ni/β-Ga₂O₃ Schottky barrier diodes fabricated using the Ge-doped drift layer exhibited good rectifying behavior with a turn-on voltage of 0.74 V, an ideality factor of 1.32, a Schottky barrier height of 1.02 eV, and a specific on-resistance of 2.49 mΩ·cm². Capacitance−voltage measurements yielded a net donor concentration of 7.7×10¹⁷ cm⁻³ and a Schottky barrier height of 1.06 eV, in good agreement with Hall and current−voltage measurements. These results demonstrate that LPCVD enables controllable Ge doping while maintaining high structural and electronic quality, establishing LPCVD-grown Ge-doped β-Ga₂O₃ as a promising platform for future high-voltage power electronic devices.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8302–8311"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222040","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":"[La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window","authors":"Cuier Deng,&nbsp;Yuhan Hu,&nbsp;Ruixi Wang,&nbsp;Jingyu Guo","doi":"10.1021/acs.cgd.6c01084","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01084","url":null,"abstract":"<p>Birefringent crystals are essential for polarization control in optical systems, yet achieving both large birefringence (Δ<em>n</em>) and a broad transmission window from ultraviolet to infrared remains a significant challenge. Here, we synthesize a novel birefringent crystal [La₃Br][GeS₄]₂ (LGSB) with ultrahigh birefringence and a broadband optical transparency window, where a trigonal-planar [La₃Br] cationic moiety serves as a structural “puppeteer” to modulate the ordered assembly of [GeS₄] tetrahedra. More notably, theoretical calculations confirm that the non-bonding S 3<em>p</em> in [GeS₄] and the non-bonding Br 4<em>p</em> in [La₃Br] are both aligned and spread along a consistent direction. These unique traits endow LGSB with exceptional birefringence (Δ<em>n</em>_obv. = 0.344@546 nm), surpassing currently reported sulfur-containing chalcogenide halides, even outperforming benchmark crystals YVO₄ (0.230@546 nm) and TiO₂ (0.300@546 nm). Meanwhile, it delivers an ultrabroad transmission range of 0.36−23.2 μm. Thus, LGSB sets a new standard for wide-bandwidth, high-anisotropy materials and shows strong prospects for multi-band optical parametric oscillators (OPOs) and advanced photonic devices.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8497–8503"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222035","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":"Li+-Induced Enhancement of Excitonic Luminescence in γ-CuBr Single Crystals Grown by the Vertical Bridgman Method","authors":"Zhijin Zhang,&nbsp;Yizhe Hu,&nbsp;Qiuyu Yu,&nbsp;Jiacheng Pan,&nbsp;Jianguo Pan,&nbsp;Shangke Pan","doi":"10.1021/acs.cgd.6c01110","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01110","url":null,"abstract":"<p>The intrinsic defects in pure γ-CuBr crystal lead to obvious nonradiative recombination, thereby significantly suppressing its ultrafast free-exciton emission. In this study, we successfully grew undoped and Li⁺-doped CuBr:<em>x</em>%Li (<em>x</em> = 0, 1, 3, 5) single crystals using the vertical Bridgman method after purifying raw materials via recrystallization. The influence of Li⁺ ion incorporation on the crystal structure and photoluminescence (PL) properties was investigated. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that Li⁺ is incorporated in the lattice of γ-CuBr. Moderate Li⁺ doping markedly enhances the near-band-edge (NBE) emission, with CuBr:3%Li composition exhibiting the highest PL intensity<span></span>approximately six times that of pure CuBr. Time-resolved PL further demonstrates an ultrafast radiative decay lifetime of 2.40 ns at 419 nm for the optimal crystal. Temperature-dependent photoluminescence (PL) measurements revealed that the thermal stability of NBE emission significantly improved after Li⁺ doping. The thermal activation energy of CuBr:3%Li is 382.6 meV.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8536–8542"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222006","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":"Flux-Grown Centimeter-Sized Sodium Niobate−Barium Titanate Solid Solution Single Crystals: Crystal Structure and Physical Properties","authors":"Haotian Zhou,&nbsp;Yongxing Wei,&nbsp;Changpeng Guan,&nbsp;Zhaotian Chen,&nbsp;Jialin Niu,&nbsp;Changqing Jin,&nbsp;Yike Cheng,&nbsp;Peijiang Li,&nbsp;Zhong Yang,&nbsp;Zengyun Jian,&nbsp;Zhonghua Dai,&nbsp;Zengzhe Xi,&nbsp;Li Jin","doi":"10.1021/acs.cgd.6c01063","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01063","url":null,"abstract":"<p>Centimeter-sized pale-yellow 0.91NaNbO₃-0.09BaTiO₃ (NN-9BT) single crystals were successfully grown by the flux method near the orthorhombic−tetragonal phase boundary of the NaNbO₃−BaTiO₃ system. The as-grown crystals display intergrowing grain features, and the maximum grain size is on the centimeter scale. Room-temperature X-ray diffraction revealed a {100}_C-oriented orthorhombic structure dominated by the <em>P</em>2₁<em>ma</em> phase. At room temperature, the crystals exhibited a remanent polarization (<em>P</em>_r) of 10 μC/cm² and a coercive field (<em>E</em>_c) of 32 kV/cm. The strain-electric field (<em>S</em>−<em>E</em>) response displayed an antisymmetric profile, which became increasingly pronounced with increasing temperature. The in situ piezoelectric coefficient (<em>d</em>₃₃) reached a maximum value of approximately 160 pC/N at 180−190 °C before decreasing sharply near 220 °C. Temperature-dependent X-ray diffraction and Raman spectroscopy revealed a stepwise structural evolution from <em>P</em>2₁<em>ma</em> to <em>Pbnm</em>(1), <em>Pbnm</em>(2), and finally <em>P</em>4/<em>mbm</em>. The transition from <em>Pbnm</em>(1) to <em>Pbnm</em>(2) involved not only doubling of the <em>b</em>-axis but also a change in the rotational modes of the Nb/TiO₆ octahedra. Impedance spectroscopy yielded an activation energy of approximately 0.986 eV, suggesting a defect-assisted thermally activated conduction mechanism.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8480–8488"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222010","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":"Halogen Effects and Anion Regulation in a Dual-Substituted FeIII-qsal Platform: Steering Abrupt to Two-Step SCO with Wide Hysteresis","authors":"Xin-Li Liu,&nbsp;Wen-Kun Yan,&nbsp;Yue Zhao,&nbsp;Yi-Fei Deng,&nbsp;Tianwei Wang,&nbsp;Yuan-Zhu Zhang,&nbsp;Xin-Yi Wang","doi":"10.1021/acs.cgd.6c00923","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00923","url":null,"abstract":"<p>Achieving abrupt, hysteretic spin crossover (SCO) requires strong cooperativity, typically engineered through supramolecular interactions. In this work, we designed a dual-halogenated Hqsal ligand, 5-F-Hqsal-5-I_q, strategically incorporating both bulky iodine and electronegative fluorine moieties. This design modulates the ligand field and, more importantly, induces strong halogen-mediated supramolecular interactions. Three Fe^III complexes, [Fe(5-F-qsal-5-I_q)₂]A·CH₃OH (A = ClO₄⁻ (<strong>1</strong>), BF₄⁻ (<strong>2</strong>), and OTf⁻ (<strong>3</strong>)), were synthesized and characterized, all adopting a similar Chain-Layer packing motif. The steric demand of the iodine atom forces the fluorine atoms on adjacent chains into closer proximity, which enhances hydrogen bonds and fluorine-mediated interactions within the 2D layers, thereby enhancing cooperativity. Notably, complex <strong>3</strong> exhibits enhanced cooperativity driven by extensive and intensified supramolecular interactions involving the iodine atoms and the OTf⁻ anion. Magnetically, <strong>1</strong> and <strong>2</strong> exhibit abrupt SCO with narrow hysteresis, while <strong>3</strong> exhibits a two-step transition with a remarkably wide and stable 57 K hysteresis (1 K/min) that expands to 64 K at 15 K/min. All complexes exhibit the LIESST effect, with <strong>3</strong> showing the most pronounced response. This study underscores how steric and electronic effects from dual-halogen substitution can be employed to modulate SCO properties, offering a rational design route to high-performance SCO materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8345–8355"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222076","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}