CrystEngComm最新文献

{"title":"Covalent organic–inorganic layered 2D CdCl2(n-hexylamine)2 and not Cd2S2(n-hexylamine)†","authors":"Pavithra Parthiban, Urmila Makhija, Rachit Pratham, Diptikanta Swain and Angshuman Nag","doi":"10.1039/D5CE00011D","DOIUrl":"https://doi.org/10.1039/D5CE00011D","url":null,"abstract":"<p >Organic ammonium cations (A<small>⁺</small>) and inorganic [PbX<small>₄</small>]<small>²⁻</small> (X: Cl, Br, I) anions bind to each other through electrostatic interactions, forming layered two-dimensional (2D) A<small>₂</small>PbX<small>₄</small> hybrid perovskites. Thus, they dissociate in water. In contrast, charge-neutral organic amines (L) can covalently bind to metal M (M: Zn, Cd), forming M<small>₂</small>Q<small>₂</small>(L) (Q: S, Se, Te) hybrid II–VI semiconductors. We attempted to explore the optoelectronic properties of such a reported hybrid II–VI compound, Cd<small>₂</small>S<small>₂</small>(<em>n</em>-hexylamine), but surprisingly it did not form. Instead, the obtained product, referred to here as product-1, is a mixture of a new layered halide compound CdCl<small>₂</small>(<em>n</em>-hexylamine)<small>₂</small> and CdS nanocrystals (NCs). The quantum confinement in ∼3 nm CdS NCs shows interesting optoelectronic properties, which were initially misinterpreted as signatures of a Cd<small>₂</small>S<small>₂</small>(<em>n</em>-hexylamine) quantum well structure. The obtained layered compound CdCl<small>₂</small>(<em>n</em>-hexylamine)<small>₂</small> crystallizes in the <em>P</em>2<small>₁</small>/<em>c</em> space group. Each Cd<small>²⁺</small> is coordinated with 4 equatorial Cl<small>⁻</small> and two axial <em>n</em>-hexylamines, forming distorted octahedra that propagate in 2D, forming the layered structure. Note that the organic and inorganic components in CdCl<small>₂</small>(<em>n</em>-hexylamine)<small>₂</small> are covalently bound (coordinate bonds), making the compound water-stable, unlike the electrostatically bound A<small>₂</small>PbX<small>₄</small> perovskites. The covalent organic–inorganic bonding nature of the layered 2D hybrid halide compounds might be explored further for designing water-stable hybrid halide perovskite-like materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 2004-2011"},"PeriodicalIF":2.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688250","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":"A photoluminescent second-order nonlinear optical molecular crystal with cold crystallization†","authors":"Xin Shen, Jun-Chao Qi, Hang Peng, Zhang-Tian Xia, Yong-Ju Bai, Hui-Ping Chen, Zhen-Yu Wang, Tian-En Yang, Yan Qin and Wei-Qiang Liao","doi":"10.1039/D4CE01322K","DOIUrl":"https://doi.org/10.1039/D4CE01322K","url":null,"abstract":"<p >Cold crystallization occurs commonly in polymers but is rarely found in small molecular crystals. Here, we report the first photoluminescent second-order nonlinear optical molecular crystal with cold crystallization, which shows crystallization upon heating at 358 K as well as green photoluminescence emission and strong second harmonic generation response with intensity comparable to that of KH<small>₂</small>PO<small>₄</small>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1381-1385"},"PeriodicalIF":2.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535719","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":"Second-harmonic generation in OP-GaAs0.75P0.25 heteroepitaxially grown from the vapor phase","authors":"Li Wang, Shivashankar R. Vangala, Stefan Popien, Marcus Beutler, J. Matthew Mann, Vladimir L. Tassev, Edlef Büttner and Valentin Petrov","doi":"10.1039/D4CE01304B","DOIUrl":"https://doi.org/10.1039/D4CE01304B","url":null,"abstract":"<p >Second-harmonic generation using femtosecond pulses at 5.5 μm with a repetition rate of 80 MHz is demonstrated in ∼500 μm-thick layers of orientation-patterned GaAs<small>_0.75</small>P<small>_0.25</small> grown using hydride vapor phase epitaxy on a structured GaAs template. The length of the sample used (∼500 μm) corresponds to only 4 quasi-phase matching periods of 8 coherence lengths.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1373-1376"},"PeriodicalIF":2.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535717","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":"Understanding the stability of the amorphous form of darifenacin†","authors":"Przemysław Nowak, Anna Pietrzak and Marta K. Dudek","doi":"10.1039/D4CE01257G","DOIUrl":"https://doi.org/10.1039/D4CE01257G","url":null,"abstract":"<p >Darifenacin (DAR) is a benzofuran derivative used in the treatment of an overactive bladder. In a neat solid phase it shows a propensity to exist in an amorphous form (DAR-A), and in this work we examined the molecular reasons standing behind this propensity. To that purpose we characterized structurally two solvated forms of DAR, a hydrate (DAR-H) and a toluene solvate (DAR-T), using single crystal X-ray diffraction and solid-state NMR spectroscopy, and conducted crystal structure prediction (CSP) calculations to compare the energetic stability of the solvated and non-solvated phases. DAR-A was found to show no preference towards particular intermolecular interactions (no local molecular ordering), a feature associated with a lower likelihood for spontaneous crystallization. The CSP landscape for neat crystal forms showed that the lowest energy structures were at the same time low density ones, a phenomenon not commonly observed for stable neat crystals. Many of these low energy structures contained voids, which is consistent with the experimental tendency of DAR to form solvated rather than neat crystal structures. Indeed, the solvated structures were found to be more energetically favourable, and this was associated with the presence of intermolecular interactions between DAR and solvent molecules, providing an energetic compensation for unfavourable conformational energies. The computational results were consistent with experimental observation of crystallization behaviour of DAR and indicate a low likelihood of ever finding a neat polymorphic form of DAR.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1927-1938"},"PeriodicalIF":2.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688229","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":"Hydrogen bonding of H2O2 molecules in crystal structures of alkali metal and tetraethylammonium nitrate peroxosolvates†","authors":"Alexander G. Medvedev, Elena A. Mel'nik, Alexey A. Mikhaylov, Nikita S. Mayorov, Tatiana A. Tripol'skaya, Ovadia Lev, Petr V. Prikhodchenko and Andrei V. Churakov","doi":"10.1039/D4CE01109K","DOIUrl":"https://doi.org/10.1039/D4CE01109K","url":null,"abstract":"<p >Peroxosolvates of nitrates remain a poorly studied class of compounds among the crystalline adducts of hydrogen peroxide and salts of inorganic acids. Herein, we report the synthesis, crystal structures, and FTIR and thermal studies of four hydrogen peroxide adducts of alkali metal and tetraethylammonium nitrates: KNO<small>₃</small>·0.5H<small>₂</small>O<small>₂</small>, RbNO<small>₃</small>·0.5H<small>₂</small>O<small>₂</small>, RbNO<small>₃</small>·0.5H<small>₂</small>O<small>₂</small>·0.5H<small>₂</small>O, and Et<small>₄</small>N<small>⁺</small>NO<small>₃</small><small>⁻</small>·2H<small>₂</small>O<small>₂</small>. The peroxosolvates of potassium and rubidium nitrates are found to be non-isomorphous. Solid state DFT calculations were performed to compare the hydrogen bond energy values of the hydrogen peroxide molecule with nitrate anions in the obtained compounds and bromide, chloride, sulfate and carbonate anions in the previously reported crystalline peroxosolvates of the corresponding salts. The calculated hydrogen bond energy values of hydrogen peroxide molecules with the anions correlate with their basicity. For the nitrate anion, these values (29.7–34.7 kJ mol<small>⁻¹</small>) are higher than those for halides and lower than for sulfate and carbonate anions. In addition, the interaction of alkali metal cations with the oxygen atom of hydrogen peroxide was analyzed, revealing a non-covalent binding.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1896-1903"},"PeriodicalIF":2.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688225","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":"Synergistic effect of built-in and polarized electric fields in BiFeO3/BiOI heterojunctions for efficient photocatalysis†","authors":"Jiangwen Bai, Jiamin Li, Jinmeng Xiang and Chongfeng Guo","doi":"10.1039/D5CE00041F","DOIUrl":"https://doi.org/10.1039/D5CE00041F","url":null,"abstract":"<p >The built-in electric field (IEF) between two components of a heterojunction has been proven to be capable of efficiently separating photogenerated carriers in photocatalysis. However, the rapid charge accumulation near the interface of the heterojunction tends to neutralize this electric field, resulting in the deterioration of the heterojunction performance. Herein, ferroelectric-based BiFeO<small>₃</small>/BiOI-<em>n</em> heterojunctions (BFO/BiOI-<em>n</em>) were prepared utilizing epitaxial growth. BFO not only endows the heterojunctions with stronger ferroelectric polarization, which was confirmed by the hysteresis loop, but also induces a significant redistribution of carriers, which maintains a stronger IEF in BFO/BiOI-<em>n</em>. Furthermore, the ferroelectric polarization of BFO was further regulated <em>via</em> corona poling and the enlarged ferroelectric polarization was also favorable to improve the photocatalytic performance. The optimal PBFO/BiOI-4 sample delivers complete degradation of RhB within 30 minutes and a hydrogen evolution rate of 150 μmol g<small>⁻¹</small> h<small>⁻¹</small>. The significantly improved photocatalytic performance is attributed to the efficient photogenerated carrier separation synergistically promoted by the IEF in the heterojunction and the polarized electric field (PEF) in BFO. This work provides a feasible scheme for designing ferroelectric-based heterojunction photocatalysts.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1837-1850"},"PeriodicalIF":2.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632291","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":"Cd(ii) complexes of 9-anthracenyl-4′-benzoate and 4-pyridyl vinyl arenes: effect of steric hindrance on the solid-state photoreactivity†","authors":"K. Mohamed Yusuf Baig and Goutam Kumar Kole","doi":"10.1039/D4CE01221F","DOIUrl":"https://doi.org/10.1039/D4CE01221F","url":null,"abstract":"<p >This study demonstrates the effect of steric hindrance on the solid-state photoreactivity investigated in four discrete complexes [Cd(<strong>9-AnBz</strong>)<small>₂</small>(<strong>4-StPy</strong>)<small>₂</small>(MeOH)<small>₂</small>]·2H<small>₂</small>O (<strong>1</strong>), [Cd<small>₂</small>(<strong>9-AnBz</strong>)<small>₄</small>(<strong>1-NVP</strong>)<small>₄</small>]·2MeOH (<strong>2</strong>), [Cd<small>₂</small>(<strong>9-AnBz</strong>)<small>₄</small>(<strong>2-NVP</strong>)<small>₄</small>] (<strong>3</strong>), and [Cd(<strong>9-AnBz</strong>)<small>₂</small>(<strong>9-AnVP</strong>)<small>₂</small>(MeOH)<small>₂</small>] (<strong>4</strong>), where <strong>9-AnBz</strong> = 9-anthracenyl-4′-benzoate, <strong>4-StPy</strong> = (<em>E</em>)-styryl-4-pyridine, <strong>1-NVP</strong> = (<em>E</em>)-1-naphthalenevinyl-4′-pyridine, <strong>2-NVP</strong> = (<em>E</em>)-2-naphthalenevinyl-4′-pyridine, and <strong>9-AnVP</strong> = (<em>E</em>)-9-anthracenylvinyl-4′-pyridine. Their structures have been determined by single-crystal XRD diffraction and the stacking of the arene-containing pyridyl-based auxiliary olefin ligands in these complexes has been analysed. The <strong>4-StPy</strong> ligands from two neighbouring complexes were found to stack in a <em>head-to-tail</em> fashion, and thus complex <strong>1</strong> was found to be photoreactive when exposed to sunlight. The process of the photodimerization reaction was further observed to exhibit a photosalient effect when investigated under UV light. With a gradual increase in the steric crowd in the arene moieties of the auxiliary ligands, complexes <strong>2–4</strong> were observed to be photo-inert. Pyridyl-based auxiliary ligands of different steric demands resulted in distinct coordination numbers, geometries, structural diversity, and solid-state photo-reactivity. Solid-state photoluminescence for all complexes <strong>1–4</strong> has been investigated.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1657-1667"},"PeriodicalIF":2.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602084","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":"Pharmaceutical salts of venetoclax with dicarboxylic and sulfonic acids: solid-state characterization and dissolution performance†","authors":"Tereza Havlůjová, Erika Hriňová, Eliška Zmeškalová, Monika Kučeráková, Luděk Ridvan and Miroslav Šoóš","doi":"10.1039/D4CE01121J","DOIUrl":"https://doi.org/10.1039/D4CE01121J","url":null,"abstract":"<p >This study focuses on enhancing the aqueous dissolution of venetoclax through salt formation. Venetoclax, a BCS class IV B-cell lymphoma-2-selective inhibitor, exhibits very low solubility and bioavailability. Given its multiple protonable groups, salt formation was explored to improve its dissolution properties. Dicarboxylic and sulfonic acids were selected as counterions for salt screening. Ten salts were synthesized and characterized using powder X-ray diffraction, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Intrinsic dissolution rate measurements demonstrated that all salts dissolve faster than the parent drug. The crystal structures of venetoclax, venetoclax fumarate, venetoclax oxalate, and venetoclax napsylate, which all solvated with acetonitrile, and unsolvated venetoclax tosylate were elucidated and described.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1816-1829"},"PeriodicalIF":2.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01121j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632289","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":"Growth, anisotropy, and spectroscopy of Tm3+ and Yb3+ doped MgWO4 crystals","authors":"Ghassen Zin Elabedine, Rosa Maria Solé, Sami Slimi, Magdalena Aguiló, Francesc Díaz, Weidong Chen, Valentin Petrov and Xavier Mateos","doi":"10.1039/D4CE01168F","DOIUrl":"https://doi.org/10.1039/D4CE01168F","url":null,"abstract":"<p >We report on an improved crystal growth process, reassessment of the orientation of the optical ellipsoid, and polarized spectroscopy of doped monoclinic magnesium monotungstate (MgWO<small>₄</small>) in a new dielectric frame. A set of crystals, including undoped, Yb<small>³⁺</small>-doped, and Tm<small>³⁺</small>-doped MgWO<small>₄</small>, were grown by the top-seeded solution growth (TSSG) method with K<small>₂</small>W<small>₂</small>O<small>₇</small> as a solvent. This approach resulted in high-quality crystals with a significantly reduced growth time compared to those grown using Na<small>₂</small>WO<small>₄</small>. The crystal structures were confirmed by powder X-ray diffraction, and the lattice parameters were determined using Le Bail fitting. We review the growth methodology and emphasize the revision of the principal optical axes orientation in this biaxial crystal which differs substantially from previous reports. Polarized Raman spectroscopy was conducted based on this revised orientation. The absorption and stimulated emission cross-sections of the studied ions were derived for the principal light polarizations, comparing these findings with existing results to validate the new dielectric frame orientation.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1619-1631"},"PeriodicalIF":2.6,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01168f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602081","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":"Synthesis, crystal growth and phase formation in the K–(Yb,Tm,Ho)–Mo–O system","authors":"Victor V. Maltsev, Elena A. Volkova, Elizaveta V. Koporulina, Nikolai N. Kuzmin, Anna I. Jiliaeva, Galina V. Kiriukhina and Daniil A. Naprasnikov","doi":"10.1039/D5CE00021A","DOIUrl":"https://doi.org/10.1039/D5CE00021A","url":null,"abstract":"<p >In the present work, the synthesis conditions and crystal growth as well as the phase transitions, morphology, and luminescence spectra of K(Yb<small>_{1−<em>x</em>−<em>y</em>}</small>Tm<small>_<em>x</em></small>Ho<small>_<em>y</em></small>)(MoO<small>₄</small>)<small>₂</small> solid solutions have been studied. The intense white emission of Tm<small>³⁺</small> and Ho<small>³⁺</small> ions was obtained in polycrystalline and single crystal samples in the range <em>x</em> + <em>y</em> = 0.01–0.02. The phase formation in the K–(Yb,Tm,Ho)–Mo–O system was studied and single crystals of K(Yb,Tm,Ho)(MoO<small>₄</small>)<small>₂</small> and (Yb,Tm,Ho)<small>₂</small>Mo<small>₃</small>O<small>₁₂</small> were grown from the melts at different temperatures. The crystals exhibit white-light luminescence excited with a 980 nm source.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1607-1618"},"PeriodicalIF":2.6,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602080","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}