Crystal Growth & Design最新文献

{"title":"Spontaneous Mirror Symmetry Breaking in Two-Step Nucleation of an Organopalladium(II) Reaction-Crystallization System","authors":"Xiaobao Zhang,&nbsp;Shuqi Luo,&nbsp;Xiaoyong Chang,&nbsp;Ning Zhou,&nbsp;Chao Zou and Wei Lu*,&nbsp;","doi":"10.1021/acs.cgd.5c0053510.1021/acs.cgd.5c00535","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00535https://doi.org/10.1021/acs.cgd.5c00535","url":null,"abstract":"<p >Homochiral crystals of a dinuclear cyclometalated palladium(II) diarylacetylide complex were grown out from an initially achiral reaction-crystallization system, wherein we have been able to identify that the spontaneous mirror symmetry breaking (SMSB) occurred in the supersaturation phase of a two-step nucleation period.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3260–3265 3260–3265"},"PeriodicalIF":3.2,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098260","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":"Trinuclear Cobalt(II)-Based Metal–Organic Framework Showing Solvent-Induced Switching to Magnetic Ordering","authors":"Yusuke Kataoka*,&nbsp;Kanami Matsubara,&nbsp;Natsumi Yano,&nbsp;Ryoji Mitsuhashi,&nbsp;Hiroshi Sakiyama and Makoto Handa*,&nbsp;","doi":"10.1021/acs.cgd.5c0043810.1021/acs.cgd.5c00438","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00438https://doi.org/10.1021/acs.cgd.5c00438","url":null,"abstract":"<p >A new self-assembled two-dimensional trinuclear cobalt-based metal–organic framework (MOF), [Co₃(CHDC)₃(DMF)_2.5(H₂O)_0.5]·(DMF)_1.5 (<b>1C</b>), which was constructed from two types of trinuclear cobalt secondary building units (Co₃–SBUs) with <i>trans</i>-1,4-cyclohexanedicarboxylate, was synthesized by a solvothermal reaction and structurally characterized by synchrotron single crystal X-ray diffraction analyses. <b>1C</b> undergoes a phase transition to an amorphous MOF (<b>1A</b>) upon heating at 160 °C, due to the desorption of DMF/H₂O molecules. Conversely, <b>1A</b> can revert back to crystalline <b>1C</b> through reflux in aqueous DMF solutions, demonstrating a reversible phase transition behavior. Magnetic susceptibility measurements of <b>1C</b> revealed that the ferromagnetic interactions are operative between Co ions within the Co₃–SBUs (<i>J</i> = +2 ∼ +5 cm^–1), which is consistent with DFT calculations indicating that the ground state of the Co₃–SBUs is <i>S</i> = 9/2. In contrast, <b>1A</b> show the antiferromagnetic interactions; χ_M<i>T</i> decreased continuously upon cooling due to the orbital contribution. That is, <b>1C</b> acts as a magnetic sponge, in which magnetic ordering switches in response to desorption and adsorption of DMF/H₂O molecules.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3570–3577 3570–3577"},"PeriodicalIF":3.2,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098133","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 Portfolio of Ciprofloxacin Hydrochloride Ionic Cocrystals with Phenolic Acids for Tailoring Dissolution and Solubility","authors":"Juan Manuel Martínez-Alejo,&nbsp;Herbert Höpfl,&nbsp;Dea Herrera-Ruiz* and Hugo Morales-Rojas*,&nbsp;","doi":"10.1021/acs.cgd.4c0171110.1021/acs.cgd.4c01711","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01711https://doi.org/10.1021/acs.cgd.4c01711","url":null,"abstract":"<p >Ciprofloxacin is a potent antibiotic used for the treatment of bacterial infections located mainly in the urinary and pulmonary tracts. In this work, we report the formation of ionic cocrystals of ciprofloxacin hydrochloride (CiHCl) in combination with phenolic acid derivatives like 2,3-dihydroxybenzoic acid (23DBA), 2,4-dihydroxybenzoic acid (24DBA), 2,5-dihydroxybenzoic acid (25DBA), 3,4-dihydroxybenzoic acid (34DBA), 3,5-dihydroxybenzoic acid (35DBA), and gallic acid (GAL). This series of phenolic acids was selected to systematically explore the impact on the biopharmaceutical properties of CiHCl originating from the formation of ionic cocrystals with species containing phenolic groups in different numbers and symmetry. The solids were obtained by solution-based crystallization (viz., slurry, reaction crystallization, solvent evaporation) and mechanochemical methods (LAG), and they were fully characterized by PXRD, TG, DSC, IR, NMR, and elemental analysis. Single-crystal X-ray diffraction studies were performed for anhydrous CiHCl and CiHCl·23DBA. Structural comparison by Hirshfeld surface and fingerprint analysis of the anhydrous and hydrated forms (CiHCl and CiHCl·H₂O) with the ionic cocrystals (CiHCl·4HBA, CiHCl·23DBA, and CiHCl·35DBA·H₂O) revealed that changes in the hydrogen bonding and π–π interactions play a fundamental role in the supramolecular organization in the solid state and the successful establishment of cocrystals. In the anhydrous salt, the chloride ion coordination environment is determined by two [N–H]⁺···Cl^– and C–H···Cl^– hydrogen bonds. In CiHCl·H₂O, CiHCl·4HBA, CiHCl·23DBA, and CiHCl·35DBA·H₂O, these interactions are partially or entirely replaced by [N–H]⁺···O, O–H···Cl^– and O–H···O hydrogen bonds with water and coformer molecules, respectively, mostly at the expense of C–H···Cl^– interactions. The presence of two available hydrogen bonding donors in the phenolic acids is essential in the formation of cocrystals, and therefore, coformers compromised in intramolecular O–H···O hydrogen bonds, such as 2HBA and 26DBA, were not successful. In most cases, dissolution rates and solubilities of the cocrystals were lower than for CiHCl·H₂O, covering overall a range of an order of magnitude. The trend found for these parameters correlates with the solubility of the coformers. The cocrystal with the most soluble coformer (35DBA) showed phase transformation, the highest dissolution rate constant, and its solubilization surpasses that of the reference salt (CiHCl·H₂O), demonstrating the utility of cocrystallization for generating a portfolio of ionic cocrystals with tailored properties.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3328–3346 3328–3346"},"PeriodicalIF":3.2,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098114","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":"Probing Macromolecular Interactions by Loss of Solvent Content in Protein Crystals: Application to the Amyloid-β Peptide Binding to Transthyretin","authors":"Diogo Costa-Rodrigues,&nbsp;José P. Leite and Luís Gales*,&nbsp;","doi":"10.1021/acs.cgd.5c0033610.1021/acs.cgd.5c00336","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00336https://doi.org/10.1021/acs.cgd.5c00336","url":null,"abstract":"<p >X-ray crystallography is commonly used to determine the structure of protein–protein complexes, revealing the atomic details of the interactions between macromolecules in the crystal. However, this technique has limited application in binary systems characterized by transient or weak interactions. Here, we demonstrate that protein crystals can still provide valuable information in such systems by assessing crystal solvent content. We applied this method to investigate the interaction between transthyretin (TTR) and the amyloid beta (Aβ) peptide, a system of interest due to transthyretin’s proposed role in the clearance of Aβ peptide, whose accumulation in the brain is associated with Alzheimer’s disease. Soaking TTR crystals separately with Aβ fragments results in distinct reductions of the crystal void volume and highlights the key sequence residues involved in binding to TTR. Our findings indicate that the middle Aβ_12–28 fragment interacts more strongly with TTR than the N- and C-terminals. Analysis of the crystal packing and solvent content indicates an equimolar interaction between transthyretin and the Aβ_12–28 peptide. This interaction likely involves surface-exposed regions of TTR, such as the thyroxine binding pocket or the dimer pocket.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3511–3517 3511–3517"},"PeriodicalIF":3.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098080","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":"Epitaxial Growth of AlGaN/AlN Strained-Layer Superlattices by Metalorganic Vapor Phase Epitaxy for Far-UV Second Harmonic Generation","authors":"Shahzeb Malik*,&nbsp;Masaaki Ito,&nbsp;Hiroto Honda,&nbsp;Ryosuke Noro,&nbsp;Kanako Shojiki,&nbsp;Hideto Miyake,&nbsp;Masahiro Uemukai,&nbsp;Tomoyuki Tanikawa* and Ryuji Katayama,&nbsp;","doi":"10.1021/acs.cgd.4c0132510.1021/acs.cgd.4c01325","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01325https://doi.org/10.1021/acs.cgd.4c01325","url":null,"abstract":"<p >Ultrathin AlN (&lt;100 nm) layers fabricated via sputtering and subsequent face-to-face annealing (SP-FFA) over sapphire substrates can be applied as templates for the growth of AlGaN/AlN-based second harmonic generation (SHG) devices due to the high crystalline quality and smooth surface. This paper provides a concise overview of the crystalline characteristics of SP-FFA and metalorganic vapor phase epitaxy. An atomic force microscopy obtained a root-mean-square (RMS) roughness of 0.13 nm after the ultrathin growth of SP-FFA AlN. Subsequently, the impact of the SP-FFA AlN template on the regrowth of AlN and AlGaN by metalorganic vapor phase epitaxy has been examined. The phenomenon of the strong composition-pulling effect for the growth of AlGaN on the SP-FFA AlN template has been discussed. Finally, the paper discusses the successful growth of Al_0.88Ga_0.12N/AlN strained-layer superlattices, while ensuring a smooth surface morphology with an RMS roughness value of 0.15 nm, which effectively reduces the scattering loss in a waveguide. The growth of the strained-layer superlattice augments the nonlinear coupling coefficient kappa by utilizing the piezoelectric field in the transverse quasi-phase matching SHG device.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3266–3273 3266–3273"},"PeriodicalIF":3.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098078","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":"[2 + 2] Cycloaddition of Halogen-Substituted Phenyl Cinnamate Derivatives: Single Crystal Structures, Stereospecificity, and Photomechanical Behaviors","authors":"Jiaxi Liu,&nbsp;Shuhan Zhang,&nbsp;Xiqiao Yang,&nbsp;Chao Chen,&nbsp;Kaiqi Ye,&nbsp;Yanbing Shen,&nbsp;Jingbo Sun* and Ran Lu,&nbsp;","doi":"10.1021/acs.cgd.4c0153810.1021/acs.cgd.4c01538","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01538https://doi.org/10.1021/acs.cgd.4c01538","url":null,"abstract":"<p >A series of new halogen-substituted phenyl cinnamate derivatives were synthesized, and their single crystal structures were obtained. Most microcrystals of these compounds were able to undergo [2 + 2] cycloaddition reactions under UV light irradiation in the solid state based on ¹H NMR experimental data before and after the irradiation. The single crystal structure, Hirshfeld surface, energy decomposition analysis, energy framework, and molecular electrostatic potential surface study of these compounds disclosed that the hydrogen bond of the halogen···H, π···π interaction played an important role in the packing arrangement. In particular, the single crystal structure of the dimers <b>D-FPCCl</b>, <b>D-FPCBr</b>, <b>D-BrPCBr</b>, <b>D-IPCCl</b>, and <b>D-IPCBr</b> was also obtained, and <b>IPCBr</b> was the highest yield of monomer conversion to dimer after 10 min of irradiation, reaching 63%. It was interesting that the distance between the double bonds in the crystal of <b>IPCCl</b> was 5.872 Å, which was greater than 4.2 Å, but the [2 + 2] cycloaddition still occurred. Most importantly, none of these phenyl cinnamate derivatives have been found to have undergone [2 + 2] cycloaddition before, and these molecules are also reported for the first time. Furthermore, the needle-like crystal of <b>IPCBr</b> and <b>BrPCCl</b> exhibited photomechanical behaviors of swing under irradiation UV light of 365 nm.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3298–3316 3298–3316"},"PeriodicalIF":3.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097892","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":"Antisolvent Crystallization of Carbamazepine Dihydrate: Comparing Constant Growth Rate, Size-Dependent Growth, and Growth Rate Dispersion Models","authors":"Vaishnavi G. Honavar,&nbsp;Ryan G. Ellis,&nbsp;Nandkishor K. Nere and Vivek V. Ranade*,&nbsp;","doi":"10.1021/acs.cgd.5c0027910.1021/acs.cgd.5c00279","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00279https://doi.org/10.1021/acs.cgd.5c00279","url":null,"abstract":"<p >Various models have been proposed to describe the kinetics of the processes involved in the continuous crystallization of pharmaceutical solutes. In many of these models, the growth rate of crystals (m/s) is assumed to be independent of the size of the crystals. While this assumption leads to reasonable correspondence between the simulated and experimental mean particle size and solute concentration at steady state, it fails to capture the spread of the particle size distribution (PSD) accurately, especially the tail toward the lower particle sizes. Two types of models, namely, dispersion of growth rate and size dependent growth rate, have been proposed for improving the accuracy in predicting PSD. In this work, we evaluated some of these variable growth rate models for simulating the continuous antisolvent crystallization of irregularly shaped carbamazepine dihydrate (CBZ-DH) crystals. The variable growth rate models (dispersion as well as size dependent growth) are implemented in a general-purpose population balance model (PBM) based on a tank-in-series framework. The PBM was used to simulate recently published experimental data from continuous antisolvent crystallization of CBZ-DH. Sensitivity analysis with respect to key parameters was carried out. Based on the comparison of the simulated and experimental results, specific recommendations on selecting a variable growth model have been made. The presented approach, model, and results will be useful for enhancing the fidelity of models of continuous crystallizers.</p><p >We evaluated the performance of variable growth models − growth rate dispersion models and size dependent growth models with reference to size independent growth models to simulate the antisolvent crystallization of carbamazepine dihydrate. Size dependent growth models were found to perform better than other models.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3253–3259 3253–3259"},"PeriodicalIF":3.2,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00279","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098005","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":"Exploring the Structural Phase Transition, Dielectric Response, and Magnetic Properties of a New Isothiocyanate-Based Dinuclear Manganese Compound","authors":"Kai-Ping Xie*,&nbsp;Wei-Ding Fan,&nbsp;Jin Wang,&nbsp;Jiong Yang,&nbsp;Zhi-Zhen Peng,&nbsp;Yan Shi,&nbsp;Zicheng Xiao,&nbsp;Yu-Bo Zou,&nbsp;Yi-Fei Deng* and Wei-Jian Xu*,&nbsp;","doi":"10.1021/acs.cgd.5c0042910.1021/acs.cgd.5c00429","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00429https://doi.org/10.1021/acs.cgd.5c00429","url":null,"abstract":"<p >The development of novel multifunctional organic–inorganic hybrid materials incorporating isothiocyanate ligands represents an ongoing challenge in chemistry and materials science. In this study, we successfully constructed a dinuclear manganese compound, [(CH₃)₃S]₅[Mn₂(SCN)₉]. This compound exhibits a remarkable order–disorder transition of the isothiocyanate ligands and (CH₃)₃S⁺ cations, which drives reversible structural phase transitions (SPTs) with a critical temperature (<i>T</i>_c) of 206 K. Simultaneously, striking step-like anomalies are observed in the dielectric constant. Magnetic investigations reveal antiferromagnetic interactions between the dinuclear Mn²⁺ ions (<i>J</i> = −6.11 cm^–1). These findings provide new theoretical foundations for designing multifunctional materials with tunable dielectric properties.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3563–3569 3563–3569"},"PeriodicalIF":3.2,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098179","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":"Microstructure and Texture of Foraminiferal Ca-Carbonate: The Different Biomineralization Strategies of Rotaliida, Robertinida, and Miliolida","authors":"Anna Sancho Vaquer*,&nbsp;Erika Griesshaber,&nbsp;Julie Meilland,&nbsp;Lurdes Fernández-Díaz,&nbsp;Xiaofei Yin,&nbsp;Jeraldine Lastam,&nbsp;Lennart de Nooijer,&nbsp;Michal Kucera and Wolfgang W. Schmahl,&nbsp;","doi":"10.1021/acs.cgd.4c0153110.1021/acs.cgd.4c01531","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01531https://doi.org/10.1021/acs.cgd.4c01531","url":null,"abstract":"<p >We report differences for shell calcite and aragonite crystallography and crystal organization for <i>Neogloboquadrina dutertrei</i> (Rotaliida), <i>Hoeglundina elegans</i> (Robertinida), <i>Pyrgo murrhina</i>, <i>Triloculina</i> sp., and <i>Quinqueloculina</i> sp. (Miliolida). Crystals were investigated with electron backscatter diffraction (EBSD) and high-resolution field-emission SEM (FE-SEM) imaging. Rotaliid and robertinid crystals have dendritic-fractal morphologies, interdigitate strongly, and are twinned. First-formed <i>N. dutertrei</i> calcite crystallites are fibrils. Arrays of these form bundles and evolve into densely mineralized crystal entities. First-formed <i>H. elegans</i> aragonite crystallites are granules. These nucleate onto a membranous template and evolve into laths and undulated laminae. The latter are stacked in parallel and generate round-shaped crystal units. <i>H. elegans</i> aragonite and <i>N. dutertrei</i> calcite have an axial-crystal-texture at nucleation onto the template. For <i>H. elegans</i>, the latter is maintained for the entire shell. For <i>N. dutertrei</i>, the axial-crystal-texture transforms to a single-crystal-texture toward distal shell surface. For <i>N. dutertrei</i>, the change in crystal texture is controlled by the crystal growth process and growth competition. Crystal growth controlled by growth competition is not observed for <i>H. elegans</i> aragonite or miliolid calcite. Miliolid calcite is not twinned. It is a meshwork of nanometer-sized single-crystal rods, interspersed by nanometer-sized single-crystal rhombohedra. At the proximal shell surface, the rods do not have preferred orientation. At the distal shell surface, the calcite is rather granular, co-oriented, and textured. For all investigated species, calcite/aragonite <i>c</i>-axis rotates with shell curvature. Despite distinct foraminiferal shell crystallographic-structural differences, we find similarity for crystal nucleation. Nonetheless, for the investigated species, crystal growth is modulated by different growth determinants.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3274–3297 3274–3297"},"PeriodicalIF":3.2,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098178","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":"Designable Fluorescent Anthracene-Based Cd-Metal–Organic Frameworks for Sensing TNP, Fe3+, and Cr2O72–","authors":"Xue Wang,&nbsp;Xiao Li*,&nbsp;Yining Wang,&nbsp;Wenxi Zhang,&nbsp;Xin Wang* and Zhong-min Su*,&nbsp;","doi":"10.1021/acs.cgd.5c0023010.1021/acs.cgd.5c00230","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00230https://doi.org/10.1021/acs.cgd.5c00230","url":null,"abstract":"<p >Here, four new luminescent Cd(II)-metal–organic frameworks(MOFs) were solvothermally synthesized: [Cd₂(tatrz)_1.5(Hidc)₂H₂O]·3H₂O (CUST-981), [Cd(tatrz)(mip)]·2H₂O (CUST-982), [Cd(tatrz)_0.5(aip)]·2DMF (CUST-983), and [Cd(tatrz)(ntp)(H₂O)₂]·H₂O (CUST-984) (tatrz = 1-(9-(1H-1,2,4-triazol-1-yl)anthracen-10-yl)-1H-1,2,4-triazole, Hidc = imidazole-4,5-dicarboxylic acid, mip = 5-methylisophthalic acid, aip = 5-aminomethylisophthalic acid, ntp = 2-nitroterephthalic acid, CUST = Changchun University of Science and Technology). Using a semirigid anthracene-based ligand as the main ligand, the structures of the MOFs were finely tuned by carefully selecting bidentate, tridentate, and tetradentate auxiliary carboxylic acid ligands. The constructed MOFs exhibit unique two-dimensional (CUST-982 and CUST-984) and three-dimensional (CUST-981 and CUST-983) structures. CUST-981–984 possess good structural stability and thermal stability. Furthermore, CUST-981–984 all exhibit satisfactory sensitivity and selectivity for the detection of Fe³⁺, Cr₂O₇^2–, and TNP. CUST-983 displays the lowest detection limits of 0.132 and 0.481 μM for Fe³⁺ and Cr₂O₇^2–, respectively. CUST-984 shows the lowest detection limit for TNP, at 0.08 μM. The possible mechanisms of fluorescence quenching during the sensing process were systematically investigated using PXRD, UV–vis, and density functional theory. This work collectively provides a solid theoretical foundation for the applications of LMOFs in the field of contaminant detection.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 10","pages":"3404–3413 3404–3413"},"PeriodicalIF":3.2,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144098072","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}