CrystEngComm最新文献

{"title":"A Ni-added polyoxometalate: synthesis, structure and catalytic performance†","authors":"Zheng-Ge Zhang, Zhen-Wen Wang, Yu Wang, Juan Chen, Yue-Lin Wang and Guo-Yu Yang","doi":"10.1039/D5CE00060B","DOIUrl":"https://doi.org/10.1039/D5CE00060B","url":null,"abstract":"<p >A Ni<small>₆</small>-added polyoxometalate, (NH<small>₄</small>)<small>_0.5</small>Cs<small>_1.5</small>K<small>₄</small>Na<small>₃</small>[Ni(H<small>₂</small>O)<small>₆</small>][{BO(OH)<small>₂</small>}<small>₂</small>Ni<small>₆</small>(OH)(H<small>₂</small>O)<small>₆</small>(SiW<small>₁₀</small>O<small>₃₇</small>)<small>₂</small>]·8H<small>₂</small>O (<strong>1</strong>), was made with the guidance of the “lacunary-directing synthesis” strategy using a hydrothermal method and characterized by single crystal/powder X-ray diffraction, solid-state UV-vis spectroscopy, FT-IR spectroscopy, and thermogravimetric analysis. The polyoxoanion of <strong>1</strong> could be conceptually constructed by the synergistic directing effect of two dilacunary B-α-SiW<small>₁₀</small>O<small>₃₇</small> fragments linked by a central [{BO(OH)<small>₂</small>}<small>₂</small>Ni<small>₆</small>(OH)(H<small>₂</small>O)<small>₆</small>]<small>⁹⁺</small> ({B<small>₂</small>Ni<small>₆</small>}) <em>via</em> Ni–O–W and Ni–O–Si linkages. The {B<small>₂</small>Ni<small>₆</small>} cluster was composed of a V-shaped {Ni<small>₆</small>} core with an angle of 54.6° and further decorated with two BO(OH)<small>₂</small> groups. Furthermore, <strong>1</strong> could be applied in the Knoevenagel condensation reaction as a Lewis catalyst and exhibited excellent catalytic activity under mild reaction conditions.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1879-1886"},"PeriodicalIF":2.6,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Epitaxial synthesis of hybrid heterostructures based on calcium–barium fluoride solid solutions on silicon substrates and X-ray diffraction studies of their lattice parameters","authors":"A. K. Kaveev, E. A. Alexeev, E. I. Belyakova, A. S. Goltaev, V. V. Fedorov, D. V. Miniv, T. B. Popova, V. A. Sharov and Sh. A. Yusupova","doi":"10.1039/D4CE00967C","DOIUrl":"https://doi.org/10.1039/D4CE00967C","url":null,"abstract":"<p >It is known that Pb<small>_{1−<em>y</em>}</small>Sn<small>_<em>y</em></small>Te materials are attractive for studies in the area of topological insulators when <em>y</em> &gt; 0.3–0.4. In this work, a family of heterostructures based on a Pb<small>_{1−<em>y</em>}</small>Sn<small>_<em>y</em></small>Te/BaF<small>₂</small>/Ca<small>_{1−<em>x</em>}</small>Ba<small>_<em>x</em></small>F<small>₂</small>/CaF<small>₂</small>/Si(111) epitaxial system was grown <em>via</em> a molecular beam epitaxy method. The lattice parameter values of each sub-layer were determined, and the nature of the elastic strains leading to the mutual inter-influence of sub-layers was estimated. The use of a Ca<small>_{1−<em>x</em>}</small>Ba<small>_<em>x</em></small>F<small>₂</small> solid solution enabled a smoother transition in the lattice constant and a reduction in tensile and compressive strains between the sub-layers compared to a heterostructure without the use of this solid solution. Thus, it was shown that the use of a metamorphic buffer layer, including a Ca<small>_{1−<em>x</em>}</small>Ba<small>_<em>x</em></small>F<small>₂</small> solid solution, improved the quality of all interfaces within the combined buffer layer by reducing the layer strain. It was observed that the barium fluoride sub-layer exhibited a smaller mismatch in lattice parameters under compressive strain than under tensile strain, which occurred in the absence of a solid solution layer. For CaF<small>₂</small> growth, a layer-by-layer Frank–van der Merwe growth mechanism was demonstrated, while for Ca<small>_{1−<em>x</em>}</small>Ba<small>_<em>x</em></small>F<small>₂</small> growth, the Stranski–Krastanov growth mechanism predominated, and for BaF<small>₂</small> growth, the Volmer–Weber island growth mechanism was observed. It was confirmed that the CaF<small>₂</small> lattice rotated at 180° relative to the silicon lattice during high-temperature growth, with subsequent retention of the solid solution and barium fluoride orientations.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1887-1895"},"PeriodicalIF":2.6,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Manipulating the surface structure of quantum dots based on dual response modes triggered by iron ions for the visualization of hydrogen sulfide with a wide detection range†","authors":"Cong Liu, Rongxiang Feng, Shidi Li, Fengyao Wu, Xiaofei Qi, Xiaohua Huang, Tianyu Bai and Shanghua Xing","doi":"10.1039/D5CE00048C","DOIUrl":"https://doi.org/10.1039/D5CE00048C","url":null,"abstract":"<p >Developing fluorescent turn-on probes to monitor hydrogen sulfide (H<small>₂</small>S) in biosystems has attracted significant attention owing to their noninvasiveness, high spatial resolution and superior signal-to-noise ratio. Considering the significant expression level of H<small>₂</small>S in living organisms, it is a great challenge to further expand the response range to several-hundred micromolar levels while maintaining excellent sensitivity for this type of probe. Herein, we proposed a surface manipulation strategy for the highly emissive CuInS<small>₂</small> quantum dots (CIS QDs) using a recognition group with multiple responses during the assay to construct an H<small>₂</small>S turn-on fluorescent probe. Results demonstrated that the designed CIS/ZnS@Fe<small>³⁺</small> nanoprobe can react with H<small>₂</small>S <em>via</em> the modes of H<small>₂</small>S-induced reduction of Fe<small>³⁺</small> and subsequent metal-sulfide precipitation of Fe<small>²⁺</small>, producing a fluorescent signal exhibiting a two-stage linear relationship with the amount of H<small>₂</small>S. As a result, it not only possessed a considerable limit of detection of 0.68 μM and high selectivity but also had an extremely wide detection range of 0–300 μM, and it was capable of H<small>₂</small>S fluorescent imaging in living cells.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1789-1795"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural diversity in 1D hydrogen-bonded chains assembled through bis(triazole) self-association†","authors":"Jordan N. Smith and Nicholas G. White","doi":"10.1039/D5CE00020C","DOIUrl":"https://doi.org/10.1039/D5CE00020C","url":null,"abstract":"<p >We show that simple phenyl-1,3-bis(triazole) groups dimerise in solution. Dimerisation of these compounds in CDCl<small>₃</small> is too strong to measure by <small>¹</small>H NMR spectroscopy, and dimerisation in 9 : 1 CDCl<small>₃</small> : d<small>₆</small>-acetone is relatively strong (<em>K</em><small>_dimerisation</small> = 1360 or 4460 M<small>⁻¹</small>, depending on whether preorganising methyl groups are absent or present, respectively). A ditopic compound <strong>1</strong> containing two bis(triazole) groups crystallises to give hydrogen-bonded chains. Four different crystal structures were obtained, all of which are 1D chains, and all of which contain small solvent-filled channels. While the overall structure and packing are similar, diversity in the hydrogen bonding arrangements is observed due to the possibility of the triazole groups adopting either <em>syn</em> or <em>anti</em> conformations.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1568-1574"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Predicting the solid–liquid phase diagram of a ternary system with cocrystal formation†","authors":"Sahar Nasrallah, Ahmad Alhadid and Mirjana Minceva","doi":"10.1039/D4CE01256A","DOIUrl":"https://doi.org/10.1039/D4CE01256A","url":null,"abstract":"<p >Cocrystals are commonly synthesized to improve a target solute's physicochemical properties. Solvent-based cocrystallization is the most widely used process to obtain cocrystals. Developing and scaling up the production of cocrystals by solvent-based methods require the knowledge of the solid–liquid equilibrium (SLE) phase diagram of the target solute/coformer/solvent system. However, the experimental determination of the complete SLE phase diagram of a ternary system at different temperatures over the entire composition range is tedious. In this work, we propose a thermodynamic approach to predict the SLE phase diagram of a ternary system with cocrystal formation. First, the solubility of the coformer and cocrystals in the solvent is measured at different temperatures. Second, these data are fitted to obtain the binary interaction parameters of the non-random two-liquid (NRTL) model. Finally, the SLE phase diagram of the target solute/coformer/solvent system at different temperatures is predicted, utilizing the activity coefficients of the components and the melting properties of the cocrystal. Two systems were used to validate the approach: choline chloride (ChCl)/catechol/acetonitrile with ChCl : catechol 1 : 1 and 1 : 2 cocrystals and tetramethyl ammonium chloride (TMACl)/catechol/acetonitrile with TMACl : catechol 1 : 1 and 1 : 2 cocrystals. The proposed approach predicted the SLE phase diagram of the two systems, unraveling the solubility of catechol and the cocrystals of the two systems in acetonitrile as well as the dissolution behavior of the cocrystals, <em>i.e.</em>, congruent or incongruent dissolution. The proposed methodology highlights the benefit of using thermodynamic modeling for cocrystal engineering and design.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1796-1805"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01256a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High phase transition temperature and photoluminescence properties in low-dimensional molecular perovskite ferroelastic crystals†","authors":"Jia-Mei Zhang, Zhe-Kun Xu, Yan Qin, Peng-Fei Li and Zhong-Xia Wang","doi":"10.1039/D5CE00012B","DOIUrl":"https://doi.org/10.1039/D5CE00012B","url":null,"abstract":"<p >Ferroelastic materials, as a relative of ferroelectric and ferromagnetic materials, have attracted great attention in developing materials with multifunctions and smart devices for many high-end realms. In this work, we synthesized two new one-dimensional ABX<small>₃</small> type molecular perovskite crystals, <em>N</em>,<em>N</em>-dimethylpropargylaminium CdCl<small>₃</small> (DMPACdCl<small>₃</small>) and <em>N</em>,<em>N</em>-dimethylpropargylaminium MnCl<small>₃</small> (DMPAMnCl<small>₃</small>). DMPACdCl<small>₃</small> undergoes a reversible <em>mmm</em>F2/<em>m</em> type ferroelastic phase transition at 358 K, accompanied by an order–disorder transition of DMPA cations. The ferroelasticity of DMPACdCl<small>₃</small> has been verified by the evolution of observable ferroelastic domains. When the B-site metal is substituted by Mn<small>²⁺</small>, the DMPAMnCl<small>₃</small> crystal exhibits structural phase transition behavior similar to that of DMPACdCl<small>₃</small> but occurs at a higher phase transition temperature (<em>T</em><small>_tr</small> = 396 K) with a significant enhancement of 38 K. Besides, DMPAMnCl<small>₃</small> emits strong red luminescence at room temperature, with a photoluminescence quantum yield (PLQY) of 20.1%. This work highlights the regulation of phase transition temperature and photoluminescence in one-dimensional molecular perovskites by B-site metal substitution and offers significant inspiration for developing multiple function coupling materials for promising optoelectronics and smart devices.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1534-1540"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interplay of hydrogen bonding and π-stacking interactions in the solid-state architecture of pranoprofen: insights from X-ray crystallography and computational analyses","authors":"Rafel Prohens, Rafael Barbas, Guadalupe Abrego and Antonio Frontera","doi":"10.1039/D4CE01279H","DOIUrl":"https://doi.org/10.1039/D4CE01279H","url":null,"abstract":"<p >We report the crystal structure of the anhydrous form of pranoprofen, a valuable non-steroidal anti-inflammatory drug, solved by direct space methodologies from synchrotron X-ray powder diffraction data. Through a detailed joint experimental and computational study we have explored the complex interplay of aromatic and hydrogen-bonding interactions present in the molecular arrangement of pranoprofen in the solid state. Cooperativity and reinforcement of π-stacking and hydrogen bonding interactions govern the singular crystal packing of pranoprofen, suggesting potential binding mechanisms with biological targets.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1742-1748"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01279h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel sandwich Ni-added polyoxometalate with nonlinear optical properties and photothermal conversion performance†","authors":"Zhen-Wen Wang, Yue-Lin Wang and Guo-Yu Yang","doi":"10.1039/D5CE00036J","DOIUrl":"https://doi.org/10.1039/D5CE00036J","url":null,"abstract":"<p >An acentric sandwich-type Ni-added polyoxometalate (NiAP), (NH<small>₄</small>)Cs<small>_7.5</small>Na<small>_0.5</small>H<small>₂</small>[Ni(H<small>₂</small>O)<small>₃</small>Ni<small>₃</small>(H<small>₂</small>O)(PW<small>₈</small>O<small>₃₁</small>)(PW<small>₉</small>O<small>₃₄</small>)]Cl·9H<small>₂</small>O (<strong>1</strong>), was synthesized using lacunary directing synthesis. Single crystal X-ray diffraction analysis revealed that <strong>1</strong> features a central Ni<small>₃</small>O<small>₄</small> cluster sandwiched between PW<small>₈</small>O<small>₃₁</small> and PW<small>₉</small>O<small>₃₄</small>. Nonlinear optical tests revealed that <strong>1</strong> exhibited a second harmonic generation response approximately 0.8 times that of potassium dihydrogen phosphate. The introduction of nickel ions with absorption in the near-infrared region significantly improved the photothermal conversion efficiency. Under 808 nm laser irradiation, the temperature of <strong>1</strong> increased by 70 °C within 90 seconds. A photothermal conversion efficiency of 20.5% was achieved. This approach offers a novel perspective on photothermal conversion.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1650-1656"},"PeriodicalIF":2.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrochloric acid-mediated mechanical synthesis of red-emitting all-inorganic zinc halides†","authors":"Siyu Li, Jiali Yao, Dayang Wang, Keke Huang, Wensheng Yang and Renguo Xie","doi":"10.1039/D4CE01243G","DOIUrl":"https://doi.org/10.1039/D4CE01243G","url":null,"abstract":"<p >Metal halides (MHs), specifically CsPbX<small>₃</small> (where X = Cl and Br), have garnered significant research interest due to excellent optoelectronic properties. However, most of these metal halides exhibit no red emission in the visible region. In this study, Cs<small>₂</small>ZnCl<small>₄</small> powders in the presence of hydrochloric acid were synthesized through mechanical milling. X-ray diffraction (XRD) analyses revealed no detectable diffraction signals before or after acid treatment, suggesting a uniform crystal structure. The initial Cs<small>₂</small>ZnCl<small>₄</small> powders displayed intrinsic blue emission centered at 486 nm, with a Photoluminescence Quantum Yield (PLQY) of approximately 5.07%. In contrast, the hydrochloric acid-treated Cs<small>₂</small>ZnCl<small>₄</small> powder exhibited bright red emission centered at 645 nm, with a PLQY of about 12.78%. The broad emission, characterized by a full width at half maximum (FWHM) of 135 nm, was attributed to self-trapped exciton (STE) emission. X-ray photoelectron spectroscopy (XPS) analysis of Cs<small>₂</small>ZnCl<small>₄</small> before and after acid treatment suggests that hydrochloric acid introduction may have induced distortions or defects in the coordination environment of Zn<small>²⁺</small> ions. This provides a valuable route for further investigation into the optical properties of other metal halides.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1503-1510"},"PeriodicalIF":2.6,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01243g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Partial and complete hydrolysis of metal complexes based on monoiminoacenaphthene-1-ones†","authors":"Anton N. Lukoyanov, Yulia V. Zvereva, Anton V. Cherkasov, Grigory Yu. Zhigulin, Nikita P. Kharitonov and Sergey Yu. Ketkov","doi":"10.1039/D4CE01199F","DOIUrl":"https://doi.org/10.1039/D4CE01199F","url":null,"abstract":"<p >During the partial hydrolysis of metal complexes with the mono-imino-acenaphthen-1-olate (<em>R</em>-mian) dianion, the nitrogen atom is protonated at the first stage, while the metal–ligand bond is preserved. Further hydrolysis leads to products whose structure depends on the reaction conditions. Hydrolysis by an excess of water leads to the formation of the products with a reduced C<img>N fragment, (amino ketones, R-mianH<small>₂</small>). The complexes based on the dianion of (<em>E</em>)-2-(2,6-diisopropylphenylimino)acenaphthylen-1(2<em>H</em>)-one (dpp-mian) are hydrolyzed by a HBF<small>₄</small> aqueous solution to give an ammonium salt containing a reduced C<img>N fragment with the proton bound to the ammonium nitrogen atom [(dpp-mainH<small>₃</small>)<small>¹⁺</small>BF<small>₄</small>]. When these compounds interact with an aqueous solution of HCl, the carbonyl group C<img>O is involved, while the acid proton coordinates to the nitrogen atom [(dpp-mainH<small>₃</small>)<small>¹⁺</small>Cl]. MP2 calculations explain the formation of different products. Hydrolysis of the metal complexes, bearing a <em>R</em>-mian radical-anion, by water produces a stoichiometric mixture of R-mianH<small>₂</small> and <em>R</em>-mian as a result of the <em>R</em>-mianH disproportionation. The reaction of <em>R</em>-mian with lithium aluminum hydride leads to the reduction of both the C<img>N and C<img>O fragments.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1749-1762"},"PeriodicalIF":2.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}