Crystal Growth & Design最新文献

{"title":"Uncovering the Solvent-Mediated Transformation Mechanism of 7-ADCA Crystal Habit at the Surface–Solvent Interface","authors":"Zhijia Hao,&nbsp;, ,&nbsp;Xiaowei Cheng*,&nbsp;, ,&nbsp;Yuan Han,&nbsp;, ,&nbsp;Shiyu Sun,&nbsp;, ,&nbsp;Baoshu Liu,&nbsp;, and ,&nbsp;Hua Sun*,&nbsp;","doi":"10.1021/acs.cgd.5c01131","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01131","url":null,"abstract":"<p >The crystal habit is a vital property indicator of crystal products. The solvent-mediated crystal habit transformation is basic and efficient. However, the effect of the solvent on the crystal habit transformation mechanism at the crystal face–solvent interface has been limited. In this study, the solvent-mediated crystal habit transformation mechanism of 7-aminodeacetoxycephalosporanic acid (7-ADCA) is explored from the perspectives of the inherent 7-ADCA crystal structure and the solvent effect at the crystal surface–solvent interface. The crystal structure of 7-ADCA is governed by weak contacts according to the Hirshfeld surface and the Independent Gradient Model based on Hirshfeld partition, revealing that its crystal growth is easily affected by solvent molecules. According to electrostatic potential, mean square displacement, diffusion coefficient, radial distribution function, interaction energy, and adsorption energy, amino of the outermost layers of molecules in binary solvent systems have difficulty diffusing from the bulk solution and adsorbing onto the (1 1 1̅) face, as predicted by the modified attachment energy model. This leads to the disappearance of this surface and the formation of rectangular crystals in the binary solvent systems. Besides, the selective diffusion and adsorption strength of solvent molecules on the radial crystal face of (0 1 1) and the axial crystal face of (1 1̅ 0) determine the formation of rectangular crystals with different aspect ratios.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8312–8324"},"PeriodicalIF":3.4,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195544","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":"Recent Advances in Metal–Organic Framework-Based Luminescent Sensors toward 3-Nitrotyrosine Biomarker","authors":"Xiaoting Li,&nbsp;, ,&nbsp;Huanrong Hao,&nbsp;, ,&nbsp;Liying Liu,&nbsp;, ,&nbsp;Hu Ren,&nbsp;, ,&nbsp;Jingrui Yin,&nbsp;, ,&nbsp;Junmu Wang,&nbsp;, ,&nbsp;Lu Zhang,&nbsp;, ,&nbsp;Xiutang Zhang*,&nbsp;, and ,&nbsp;Liming Fan*,&nbsp;","doi":"10.1021/acs.cgd.5c01152","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01152","url":null,"abstract":"<p >3-Nitrotyrosine (3-NT), as a specific biomarker of protein oxidative stress damage, is of great significance in the early diagnosis of various diseases. This review systematically summarizes the latest research progress and specific applications of metal–organic framework (MOF)-based luminescent sensors for detecting 3-NT in aqueous media and biological samples. It focuses on the classification and detection capacity of MOF-based 3-NT luminescent sensors. Besides, the main sensing mechanisms, including structural collapse (SC), photoinduced electron transfer (PET), fluorescence resonance energy transfer (FRET), competition absorption (CA), internal filtration effect (IFE), and dynamic quenching effect (DQE), are analyzed in depth. This review critically assesses current research progress, challenges, and future directions of MOF-based 3-NT detection, offering valuable insights for developing highly sensitive and selective MOF-based luminescent sensors. These insights will be instrumental in steering the field toward innovative and practical solutions, facilitating the design of sensors with enhanced performance and broader applicability.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"7880–7902"},"PeriodicalIF":3.4,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195683","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":"Post-Synthetic Modification of a Stepwise-Assembled [3 × 3] {Co9} Grid with Heterometallic Cd(II) and Homometallic Co(II) Salts","authors":"Gui-Quan Guo*,&nbsp;, ,&nbsp;Hong-Da Zhang,&nbsp;, ,&nbsp;Ye Tao,&nbsp;, ,&nbsp;Yu-Ting Jing,&nbsp;, ,&nbsp;Xiao Kang,&nbsp;, ,&nbsp;Hai-Ye Li*,&nbsp;, and ,&nbsp;Fu-Ping Huang*,&nbsp;","doi":"10.1021/acs.cgd.5c00853","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00853","url":null,"abstract":"<p >The controllable construction and assembly of sophisticated aggregates with specific metal centers or skeletons has become a hot topic in coordination chemistry. However, monitoring the assembly process remains a significant challenge. In this paper, the stepwise formation of a {Co₉} grid with a [3 × 3] skeleton was monitored by electrospray ionization mass spectrometry (ESI–MS). Based on the observed intermediates, a possible formation pathway was proposed as follows: [Co₂L₂] → [Co₃L₂] → [Co₄L₃] → [Co₅L₃] → [Co₆L₄] → [Co₇L₄] → [Co₈L₅] → [Co₉L₆]. From the {Co₉} grid precursor, homometallic {Co₉Co₂} and heterometallic {Co₉Cd₂} clusters with similar skeletons were prepared from the postsynthetic modification strategy when dotted with para-magnetic Co²⁺ ions and dia-magnetic Cd²⁺ ions. Furthermore, the detailed structures of {Co₉Co₂} and {Co₉Cd₂} were characterized by single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP–MS), scanning electron microscopy coupled (SEM) with energy-dispersive X-ray spectroscopy (EDS), and ESI–MS. Compared with {Co₉} precursor, the magnetic signal of {Co₉Co₂} was enhanced after postmodificated with paramagnetic Co(II) ions, but in <b>{Co</b>_<b>9</b><b>Cd</b>_<b>2</b><b>}</b>, which keep silence upon the introducing of diamagnetic Cd(II) ions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8100–8107"},"PeriodicalIF":3.4,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195593","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":"Optimizing Conditions for Crystalline Spherical Cluster Formation Using 5-Hydroxynicotinic Acid: An Experimental and Theoretical Approach","authors":"Catarina V. Esteves*,&nbsp; and ,&nbsp;Fábio Jr. F. S. Henrique*,&nbsp;","doi":"10.1021/acs.cgd.5c00748","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00748","url":null,"abstract":"<p >This manuscript provides novel insights into the optimization of synthetic procedures to obtain crystalline spherical clusters using 5-hydroxynicotinic acid (5HNA). It meticulously explores and identifies the most favorable conditions for producing spherical clusters of 5HNA. The systematic screening of various synthetic conditions has led to the successful formation of these clusters. This work not only contributes to the field of synthetic chemistry but also opens up new avenues for the potential applications of 5HNA spherical clusters. Such clusters have diverse diameters depending on the solvent and the synthesis conditions. The clusters were characterized by optical microscopy, scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Possibly the clusters were formed by a self-assembly process driven by hydrogen bonding and π–π interactions between the 5HNA molecules. The solvents ought to play a relevant role in such self-assembly process. The clusters exhibit different crystallinity depending on the solvent. Such clusters could be used as building blocks for materials with potential applications in a multitude of fields. To unveil the role of solvents in the process, complementary molecular dynamics simulations revealed that solvation significantly influences the aggregation behavior of 5HNA in both its hydroxy and zwitterionic forms. Polar aprotic solvents, particularly DMSO, THF, and ethyl acetate, promote better solvation and reduce aggregation for the hydroxy form and Zwitterion 1. In contrast, aqueous environments favor clustering due to hydrogen bonding and π–π stacking between 5HNA molecules. Zwitterion 2, however, shows stronger solvation in water, especially around its ionic groups, while aprotic solvents tend to promote aggregation through enhanced ionic interactions and π–π stacking. Among all solvents studied, DMSO stands out as the only one capable of effectively solvating all three forms of 5HNA, underscoring its unique ability to stabilize distinct molecular states and potentially influence the self-assembly and crystallinity of the resulting aggregates.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8060–8072"},"PeriodicalIF":3.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195665","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":"Pyrazine π-Hole Interaction Preference in Crystal Structures and Spectroscopic Properties of Crystalline C8/C9 Alkyl-1H-5,6,10b-triazaacephenanthrylene-2-carbonitrile","authors":"Katarzyna Ostrowska*,&nbsp;, ,&nbsp;Igor Bożek,&nbsp;, ,&nbsp;Katarzyna M. Stadnicka,&nbsp;, ,&nbsp;Piotr Goszczycki,&nbsp;, ,&nbsp;Mateusz Brela,&nbsp;, ,&nbsp;Michał Liberka,&nbsp;, ,&nbsp;Agnieszka Węgrzyn,&nbsp;, ,&nbsp;Kamil Banasiuk,&nbsp;, ,&nbsp;Paweł Ręka,&nbsp;, and ,&nbsp;Jarosław Grolik,&nbsp;","doi":"10.1021/acs.cgd.5c01009","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01009","url":null,"abstract":"<p >The cooperative electrostatic and dispersive interactions of the pyrazine π-hole in fused triaazaacephenanthrylene (<b>TAAP</b>) systems influence the crystal structures and spectroscopic properties of solid <b>TAAP</b> and <b>TAAP</b> derivatives (8/9-tert-Bu, 8,9-diMe, and N5-4-Cl/OEtC₆H₄). In crystalline phases, the pyrazine π-hole (Cg3) induces face-to-face oriented centrosymmetric dimer formation by selecting either (1) a donor partner from the conjugated electron pair of the trivalent nitrogen atom N10b(sp²) in <b>TAAP</b>, (2) π-electrons of the imine C1═N11(sp²)–H11 moiety (in some <b>TAAP</b> derivatives), or (3) lone pair (lp) interactions of the solvate dioxane oxygen (O) atoms (sp³) in a centrosymmetric tetrameric cluster [comprising four (9-<i>tert</i>-Bu<b>TAAP</b>) molecules and a dioxane molecule]. The calculated energy of the electrostatic noncovalent interaction between the dioxane lp and pyrazine π-hole was −4.64 kcal/mol, and the dispersion energy was −8.11 kcal/mol (with a Cg3···O separation of 3.170 Å). The electrostatic energy of one 9-<i>tert</i>-Bu<b>TAAP</b> molecule in a centrosymmetric dimer was −6.23 kcal/mol, and the dispersion energy was −16.6 kcal/mol, with a Cg3···N11 separation of 3.080 Å. After changing the donor partner to an amide carbonyl group that competes with imine, the two methyl groups at positions 8 and 9 of <b>TAAP</b> caused the mutual orientation of the two dimer molecules to change from a centrosymmetric face-to-face relationship to parallel stacked molecules. In the stack, the strong dispersion (−16.9 kcal/mol) and electrostatic energies (including dipole–dipole interactions, −8.15 kcal/mol) influenced the carbonyl O atom interactions with Cg3 (separation of 3.414 Å) and the pyrazine C5a═N6 bond (3.196 Å).</p><p >The pyrazine π-hole interaction with π-type donors, i.e., imine nitrogen, carbonyl, conjugated trivalent nitrogen, and oxygen lone pair (lp), stabilizes the formation of centrosymmetric dimers with a head-to-tail arrangement, dimer stacks, translational stacks, or centrosymmetric tetrameric clusters. Fluorescence property of crystalline phases is modulated by pyrazine π-hole interaction preference. A relevant effect was observed for the π-hole interaction with the electron lp from the dioxane oxygen atom.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8188–8195"},"PeriodicalIF":3.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.5c01009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ladder-Type Cu(II) Coordination Polymer with π–π Stacking of Planar Blatter Radical Ligands: Structural and Magnetic Characterization","authors":"Hemant K. Singh,&nbsp;, ,&nbsp;Kayla M. Smith,&nbsp;, ,&nbsp;Jeremy M. Rawson,&nbsp;, ,&nbsp;Bruno Camargo,&nbsp;, ,&nbsp;Ethan S. Pollett,&nbsp;, ,&nbsp;Oleksandr Hietsoi,&nbsp;, ,&nbsp;Andrienne C. Friedli,&nbsp;, and ,&nbsp;Piotr Kaszyński*,&nbsp;","doi":"10.1021/acs.cgd.5c01115","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01115","url":null,"abstract":"<p >The synthesis of two C(2)-pyridyl derivatives of the planar Blatter radical was developed by using the tris(trimethylsilyl)silane (TTMSS)-assisted cyclization of appropriate iodoarenes. These monodentate paramagnetic ligands were characterized by spectroscopic (UV–vis and electron paramagnetic resonance (EPR)) and electrochemical methods and reacted with (pdc)Cu(H₂O)₃. A complex containing the 3-pyridyl group was characterized structurally, revealing novel polymeric Cu–O–Cu–O ladders separated with slipped stacks of radical ligands. Superconducting quantum interference device (SQUID) magnetometry of this complex demonstrated strong antiferromagnetic interactions between the radicals and largely isolated Cu(II) ions. Analysis of the magnetic data with the Hatfield model, assuming two isolated one-dimensional (1D) alternating Heisenberg chains, gave <i>J</i>_RR/<i>k</i>_B = −1200 K and α_RR = 0.4 for the paramagnetic ligand stacks, and <i>J</i>_CuCu/<i>k</i>_B = −3.5 K and α_CuCu = 0.9 for the Cu(II) ion chains. Analysis of the experimental data was augmented with density functional theory (DFT) calculations.</p><p >(pdc)Cu(II) complex with a planar Blatter radical forms a novel ladder-type linear chain with adjacent slipped stacks of radicals exhibiting separate magnetic interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8289–8299"},"PeriodicalIF":3.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.5c01115","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on the Formation Mechanism of Pit Defects and Their Influence on Magneto-optical Properties in (TbYbBi)3Fe5O12 Crystals Grown by the LPE Method","authors":"Tengbo Chen,&nbsp;, ,&nbsp;Yuxi Yu*,&nbsp;, ,&nbsp;Zhong Luo*,&nbsp;, and ,&nbsp;Shuyuan Zhao,&nbsp;","doi":"10.1021/acs.cgd.5c00345","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00345","url":null,"abstract":"<p >In recent years, with the rapid development of optical transmission networks and data center construction, higher demands have been placed on the stability of magneto-optical crystal materials. To reduce defects in the growth of rare-earth iron garnets and improve the stability of their magneto-optical properties, this study explored the formation mechanism of pit defects and their impact on the properties of rare-earth iron garnet crystals. In this paper, a series of high magneto-optical quality 4-in. thick rare-earth iron garnet single-crystal films with the composition (TbYbBi)₃Fe₅O₁₂ were successfully grown by liquid-phase epitaxy. Etching the crystals in high-concentration hydrochloric acid yielded corrosion pits with regular hexagonal shapes, and detection showed that the Pt content in these pits was 15%, which is much higher than that in other areas outside the pits. Moreover, by combining the morphologies of pit defects at different thicknesses, the formation and development mechanisms of pit defects were clarified. Tests confirmed that pit defects have no significant impact on the magneto-optical properties of the crystal at specific wavelengths and temperatures. However, they reduce the stability of (TbYbBi)₃Fe₅O₁₂ crystals in environments with variable wavelengths and temperatures: specifically, the wavelength coefficient increased by 4% at 1550 nm, and the temperature coefficient rose by approximately 11% at 60 °C.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"7933–7940"},"PeriodicalIF":3.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195609","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":"Synthesis of Two Structurally Distinct Cu-MOFs Regulated by Imidazole and Their Proton Conducting Properties","authors":"Xiang Li,&nbsp;, ,&nbsp;Shiyu Wei,&nbsp;, ,&nbsp;Xin He*,&nbsp;, ,&nbsp;Qiuyue Wang,&nbsp;, ,&nbsp;Jian Zhou*,&nbsp;, ,&nbsp;Chao Huang,&nbsp;, and ,&nbsp;Shunlin Zhang*,&nbsp;","doi":"10.1021/acs.cgd.5c01108","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01108","url":null,"abstract":"<p >Developing high-performance proton conductors with robust stability remains a challenge in fuel cell technology. This study presents two copper-based metal–organic frameworks synthesized via imidazole-regulated assembly, showcasing the structural modulation effect of imidazole dosage on proton conduction properties. By adjusting the imidazole/Cu²⁺ molar ratio, we obtained two distinct frameworks: Cu-DSBPDC-1D (1D chain structure with [Cu₃(Im)₄(COO)₂] clusters) and Cu-DSBPDC-2D (2D layered structure with [Cu₉(μ₃-OH)₆(μ₂-H₂O)₄(COO)₆(Im)₈] rod-like SBUs). The 2D framework features hydrophilic channels decorated with sulfonate groups, forming continuous hydrogen-bond networks for proton transport. Both MOFs exhibit exceptional stability in boiling water and pH 3–11 solutions. Notably, Cu-DSBPDC-2D achieves a proton conductivity of 8.14 × 10^–3 S cm^–1 at 85 °C and 95% RH, retaining 90% of its initial conductivity over 72 h. Isotope-effect measurements and the moderate activation energy (0.466 eV) indicate that proton transport is mediated by sulfonate-water hydrogen bonds, operating within a regime where Grotthuss and Vehicle mechanisms coexist. This work demonstrates imidazole as a dual-functional modulator for both structural assembly and proton conduction pathways, offering a rational design strategy for stable MOF-based proton conductors.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8278–8288"},"PeriodicalIF":3.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195667","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":"Effects of Solvents on Spherical Crystals of Minoxidil","authors":"Chenwei Geng,&nbsp; and ,&nbsp;Jingtao Wang*,&nbsp;","doi":"10.1021/acs.cgd.5c00585","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00585","url":null,"abstract":"<p >Minoxidil, a topical vasodilator primarily used to treat androgenetic alopecia, has a huge market but remains underexplored in the control of its spherical crystals. Spherical crystal structure is a vital morphology due to its superior powder characteristics in pharmaceutical manufacturing. Even though solvent-induced single crystals have been well studied, there have been few studies on the solvent-mediated morphology of spherical aggregates. In this paper, several kinds of spherical crystals, such as plate crystal aggregates, nanocrystal aggregates, and core–shell aggregates, are prepared in alcoholic solvents with different carbon chain lengths. Particularly, spherulite aggregates (SLA), which are observed for the first time, are produced in a <i>n</i>-butanol–ethyl acetate mixture. Also, the growth mechanism of SLA is analyzed in detail, and it is found that the addition of ethyl acetate could change the morphology of spherulites and promote agglomeration between them compared to pure solvent systems without ethyl acetate. In addition, the method of generating supersaturation is significant by specifying the morphology of the spherulite. The flowability and other powder properties of SLA are also investigated, with a 15.8% reduction in the repose angle and 24.7% of the Hausner ratio. Furthermore, this paper reports a unique butterfly-shaped crystal of minoxidil, which undergoes a spontaneous growth in a homogeneous solution, not from agglomeration.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8010–8020"},"PeriodicalIF":3.4,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195646","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":"High-Entropy Phosphate Synthesis: Advancements through Automation and Sequential Learning Optimization","authors":"Stephanos Karafiludis,&nbsp;, ,&nbsp;Jacob Standl,&nbsp;, ,&nbsp;Tom W. Ryll,&nbsp;, ,&nbsp;Alexander Schwab,&nbsp;, ,&nbsp;Carsten Prinz,&nbsp;, ,&nbsp;Jakob B. Wolf,&nbsp;, ,&nbsp;Sabine Kruschwitz,&nbsp;, ,&nbsp;Franziska Emmerling,&nbsp;, ,&nbsp;Christoph Völker,&nbsp;, and ,&nbsp;Tomasz M. Stawski*,&nbsp;","doi":"10.1021/acs.cgd.5c00549","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00549","url":null,"abstract":"<p >Transition metal phosphates (TMPs) are extensively explored for electrochemical and catalytical applications due to their structural versatility and chemical stability. Within this material class, novel high-entropy metal phosphates (HEMPs)─containing multiple transition metals combined into a single-phase structure─are particularly promising, as their compositional complexity can significantly enhance functional properties. However, the discovery of suitable HEMP compositions is hindered by the vast compositional design space and complex or very specific synthesis conditions. Here, we present a data-driven strategy combining automated wet-chemical synthesis with a Sequential Learning App for Materials Discovery (SLAMD) framework (Random Forest regression model) to efficiently explore and optimize HEMP compositions. Using a limited set of initial experiments, we identified multimetal compositions in a single-phase crystalline solid. The model successfully predicted a novel Co_0.3Ni_0.3Fe_0.2Cd_0.1Mn_0.1 phosphate octahydrate phase, validated experimentally, demonstrating the effectiveness of the machine learning approach. This work highlights the potential of integrating automated synthesis platforms with data-driven algorithms to accelerate the discovery of high-entropy materials, offering an efficient design pathway to advanced functional materials.</p><p >A data-driven strategy combining automated wet-chemical synthesis with a sequential learning framework was used to efficiently explore and optimize high-entropy metal phosphate compositions. Based on a limited set of initial experiments, the model successfully predicted a novel Co_0.3Ni_0.3Fe_0.2Cd_0.1Mn_0.1 phosphate octahydrate phase, which was validated experimentally, demonstrating an accelerated discovery pathway for advanced functional materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"7989–8001"},"PeriodicalIF":3.4,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.5c00549","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}