CrystEngComm最新文献

{"title":"Effect of metal substitution on polymorphism and flexibility of 1D coordination polymers.","authors":"Kyriaki Koupepidou, Asif Raza, Tao He, Alan C Eaby, Soumya Mukherjee, Michael J Zaworotko","doi":"10.1039/d6ce00723f","DOIUrl":"10.1039/d6ce00723f","url":null,"abstract":"<p><p>Coordination polymers (CPs) can exhibit significant changes in properties when they adopt different polymorphs. Here, we show that metal substitution can alter the polymorphic outcome and framework stability of a one-dimensional (1D) CP. We report two packing polymorphs of a Cu(ii)-based CP, constructed from 1,3-bis(1<i>H</i>-imidazol-1-yl)benzene (bib, 1), namely polymorphs A and B of {[Cu(bib)₂(H₂O)][SiF₆]} _<i>n</i> , <b>[SP-1-Cu-H₂O][SIFSIX]-A</b> and <b>[SP-1-Cu-H₂O][SIFSIX]-B</b>, wherein extra-framework SiF₆ ^2- (<b>SIFSIX</b>) anions are hydrogen-bonded to coordinated aqua ligands (H₂O). The polymorphs comprise spiro (<b>SP</b>) loops arising from the bent conformation of the linker ligand (bib), but differ in the packing of their 1D chains. The methanol (MeOH) precursor of polymorph <b>A</b>, {[Cu(bib)₂(CH₃OH)₂][SiF₆]} _<i>n</i> , <b>[SP-1-Cu-2MeOH][SIFSIX]-A</b>, crystallised concomitantly with <b>[SP-1-Cu-H₂O][SIFSIX]-B</b> and converted to <b>[SP-1-Cu-H₂O][SIFSIX]-A</b> on exposure to air, through a single-crystal-to-single-crystal replacement of methanol by water. Metal substitution from Cu(ii) to Zn(ii) afforded only one crystalline phase, <b>[SP-1-Zn-2MeOH][SIFSIX]-A</b>, which underwent a phase transformation to <b>[SP-1-Zn-2H₂O][SIFSIX]-A</b> upon heating at 373 K under vacuum and subsequent exposure to air. Although the <b>A</b> polymorph of Cu(ii) was not stable to activation, the Zn(ii) analogue was successfully activated and analysed by gas (CO₂ at 195 and 298 K) and vapour (water at 300 K) sorption. The insights presented herein demonstrate how metal substitution may affect polymorphic landscapes and alter the activation behaviour of 1D CPs.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" ","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13735481/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149339922","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":"Quantitative approaches to understanding conformational flexibility in crystalline sponges.","authors":"Robert C Carroll, Eleanor M Soper, James E Pearce, Roohollah Hafizi, Alexandra Longcake, Adam P Cotterill, Neil J Wells, Michael J Hall, Michael R Probert, David C Harrowven, Graeme M Day, Simon J Coles","doi":"10.1039/d6ce00383d","DOIUrl":"10.1039/d6ce00383d","url":null,"abstract":"<p><p>The crystalline sponge (CS) method has expanded the capabilities of single crystal X-ray diffraction (SCXRD) chemical structure determination and analysis to liquid or oily compounds. Guest molecules encapsulated within the porous metal-organic framework (MOF) have variable intermolecular interaction strengths, both with the pore and other guest molecules, and often exhibit multiple molecular conformations. Quantification and understanding of these features has previously proved challenging and thus limited the insights available from structural models. Through combination of the CS method, conventional SCXRD, Nuclear Magnetic Resonance spectroscopy, single-molecule and periodic DFT, and energy calculations based on electron density, we determine intra- and intermolecular energy changes across a spectrum of physical environments. We explore the MOF pore environment experienced by a systematic family of small organic molecules and showcase the tools available for quantification of these complex systems.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" ","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13678619/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226749","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":"Generating, visualizing and tuning π-π interactions in metal-induced supramolecular assembly.","authors":"Giau Le-Hoang, Laure Guénée, Claude Piguet","doi":"10.1039/d6ce00611f","DOIUrl":"10.1039/d6ce00611f","url":null,"abstract":"<p><p>This work emphasizes the role of metal complexation for controlling and tuning static/dynamic π-stacked organizations responsible for the programmed light emission of the bichromophoric pyrene-terimine ligand <b>L2</b> upon photoexcitation. Its binding to the closed-shell trivalent yttrium guest [Y(hfac)₃] (hfac = 1,1,1,5,5,5-hexafluoro-pentane-2,4-dione) provides a diamagnetic heteroleptic [<b>L2</b>Y(hfac)₃] adduct for which the static intramolecular pyrene-pyrene excimer emission operating in the free ligand <b>L2</b> is transformed into a dynamic intramolecular pyrene-pyrene excimer emission in the resulting complex. The transition from static-to-dynamic intramolecular excimers results in an enhanced sensitivity toward interactions with electron-poor nitrobenzene guests, which is supported by a considerable Stern-Volmer quenching constant measured for [<b>L2</b>Y(hfac)₃]. This demonstrates that the metal-directed organization of the polyaromatic ligand in [<b>L2</b>Y(hfac)₃] can boost the excimeric chemical sensing of target aromatic analytes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" ","pages":"5808-5822"},"PeriodicalIF":2.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13622079/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149078970","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":"Room-temperature single-photon emission from III-nitride nanowire quantum dots: towards realization of the photonic qubit-based quantum computer","authors":"Swagata Bhunia, Soumyadip Chatterjee, Ayan Majumder, Kasturi Saha, Suddhasatta Mahapatra and Apurba Laha","doi":"10.1039/D5CE01123J","DOIUrl":"https://doi.org/10.1039/D5CE01123J","url":null,"abstract":"<p >III-nitride nanowire quantum dots (NWQDs) are in high-demand due to their ability to emit single photons at room temperature across the entire UV to visible wavelength range. Although tremendous progress has been made over the past decade, the efficiency of these QDs has not improved significantly. This limitation arises because true lateral confinement was difficult to achieve owing to challenges in reducing the QD diameter to the radial confinement limit. Furthermore, the presence of a giant built-in potential in NWQDs has restricted their fast operation. In this review article, we present the evolution of the III-nitride NWQD field and discuss how these challenges have been addressed to realize high-efficiency single-photon sources. Towards the end of the article, we demonstrate how these NWQDs can be leveraged to build up a photonic qubit-based quantum computer, which will be capable of operating at room temperature.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3815-3832"},"PeriodicalIF":2.4,"publicationDate":"2026-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336601","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":"The structural role of the carbonyl bridge in substituted pyridine derivatives: crystallographic and computational insights towards butyrylcholinesterase recognition","authors":"Keshav Kumar Harish, Omantheswara Nagaraja, Mohankumar Devaraju, Jagadeesh Prasad Dasappa, Honnappa Nagarajaiah, Divya Suresh, Vindu Vahini M. and Mahendra Madegowda","doi":"10.1039/D6CE00189K","DOIUrl":"https://doi.org/10.1039/D6CE00189K","url":null,"abstract":"<p >The present study is focused on a structure-guided investigation of the pyridine-based scaffold, 1-(3,5-diphenylpyridin-2-yl)ethan-1-one. The study is designed to probe how substitution variation influences the molecular conformation, crystal packing, electronic structure, and biological recognition. The rigid 3,5-diphenyl substitution limits rotational flexibility around the pyridine–carbonyl linkage, providing a structurally defined platform in which substituent-dependent effects are systematically evaluated. Four representative derivatives (<strong>MK1–MK4</strong>), bearing electron-rich 3,4-dimethoxyphenyl, halogenated dichlorophenyl, hetero aromatic thiophen-2-yl, and extended aromatic naphthyl substituents, were selected to assess substituent-dependent structural variation. Single-crystal X-ray diffraction analysis revealed that <strong>MK1</strong>, <strong>MK2</strong>, and <strong>MK3</strong> crystallize in the monoclinic space group, whereas the naphthalene-substituted derivative <strong>MK4</strong> adopts a triclinic crystal system. The torsional analysis indicates that the carbonyl bridge exhibits substituent-dependent conformational variation. The presence of the carbonyl group (C<img>O) facilitated hydrogen-bond interactions, contributing to overall molecular stabilisation, while also influencing intramolecular charge distribution and potential enzyme binding. Computational DFT analyses revealed differences in π-delocalization and donor–acceptor interactions across the series, with <strong>MK3</strong> showing the most consistent electronic interaction. Molecular docking against human butyrylcholinesterase (hBChE), benchmarked against the co-crystal ligand 5HF, identifies <strong>MK3</strong> as the compound with the highest binding affinity for the enzyme. Subsequent 100 ns molecular dynamics simulations confirmed that <strong>MK3</strong> retained dynamic stability, reflected by reduced ligand <em>R</em><small>_g</small>, SASA, and MOLSA, indicating compact, solvent-shielded binding. Overall, the structural findings provide insight into how substituent-dependent conformational variation may relate to differences in enzyme binding behaviour across the series.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 24","pages":" 3707-3732"},"PeriodicalIF":2.4,"publicationDate":"2026-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148285375","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":"The ordered organization of hydrogen-bonded organic macrocycles into a permanently porous framework","authors":"Peng Cui, Cailan Chen, Kaihao Mo, Hanyu Zhang and Qiang Zhu","doi":"10.1039/D6CE00249H","DOIUrl":"https://doi.org/10.1039/D6CE00249H","url":null,"abstract":"<p >A hydrogen-bonded organic framework (HOF) was obtained <em>via</em> the formation of a cyclic dimer hydrogen-bonded organic macrocycle (HOM) through rational molecular design. The ordered arrangement of HOMs formed permanently porous 1D channels in the HOF. These channels exhibited the selective adsorption of naphthalene.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3838-3842"},"PeriodicalIF":2.4,"publicationDate":"2026-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336603","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":"Comment on “A cooperation molecular recognition study: syntheses and analysis of supramolecular assemblies of tetrafluoroterephthalic acid with some aza compounds” by L. Wang, L. Zhao, Y. Hu, W. Wang, R. Chen and Y. Yang, CrystEngComm, 2013, 15, 2835","authors":"Szymon Kamil Araj, Dariusz Maciej Pisklak and Łukasz Szeleszczuk","doi":"10.1039/D6CE00131A","DOIUrl":"https://doi.org/10.1039/D6CE00131A","url":null,"abstract":"<p >This is a Commentary on a paper by Lei Wang <em>et al.</em> (CrystEngComm, 2013, <strong>15</strong>, 2835). The protonation state of 2-aminopyrimidine in the crystal structure deposited as REXNIT has been re-examined using periodic density functional theory (DFT) calculations. Motivated by recent literature suggestions questioning the assignment of protonation at the exocyclic amino group, several alternative protonation scenarios were systematically explored within the experimental crystal framework, allowing full relaxation of atomic positions and unit cell parameters. The results demonstrate that protonation at the ring nitrogen N1 represents the only robust and energetically preferred configuration, corresponding to a well-defined global minimum. Protonation at N3 leads to an unstable local minimum that is highly sensitive to the initial proton placement, while protonation at oxygen atoms results in spontaneous proton transfer to N1 during geometry optimization, in some cases yielding locally trapped lattice configurations. These findings provide quantitative support for reconsidering the protonation assignment in REXNIT and illustrate the value of periodic theoretical methods for validating crystallographic models involving proton transfer.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 24","pages":" 3803-3806"},"PeriodicalIF":2.4,"publicationDate":"2026-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148285401","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":"Nested icosahedral Na4@Ln12@L20 nanocages with a {Na4} parallelogram core and a {L20} dodecahedral shell","authors":"Bei Hu, Guo-Xu Li, Li Zhu, Hui-Hui Yu, Yi-Cong Lou, Shu-Ying Luo, Fu-Pei Liang and Kai Wang","doi":"10.1039/D6CE00362A","DOIUrl":"https://doi.org/10.1039/D6CE00362A","url":null,"abstract":"<p >The first family of triple-layered nested lanthanide icosahedral nanocages, which feature a unique concentric architecture bearing a {Na<small>₄</small>} parallelogram core, a {Ln<small>₁₂</small>} icosahedral skeleton and a {L<small>₂₀</small>} dodecahedral shell (Ln = Gd, Dy; L = ligand), have been constructed. Magnetocaloric effect and dual magnetic relaxation behaviour are observed in Gd- and Dy-analogs, respectively.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3833-3837"},"PeriodicalIF":2.4,"publicationDate":"2026-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336602","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":"Copper(i) iodide complexes based on [Cu5I7]2− units and cationic organic ligands for X-ray scintillation and imaging","authors":"Qian Wu, Zhen-Zhong Lu and Rui Zhang","doi":"10.1039/D6CE00336B","DOIUrl":"https://doi.org/10.1039/D6CE00336B","url":null,"abstract":"<p >Copper(<small>I</small>) iodide complexes represent a kind of promising scintillator due to their high luminescence efficiency, low toxicity, cost-effectiveness, and high atomic number of iodine, which enhances X-ray absorption. Herein, we report two copper(<small>I</small>) iodide complexes, Cu<small>₅</small>I<small>₇</small>(Ted-Pre)<small>₂</small> (<strong>1</strong>) and Cu<small>₅</small>I<small>₇</small>(Ted-EA)<small>₂</small> (<strong>2</strong>), constructed from anionic [Cu<small>₅</small>I<small>₇</small>]<small>²⁻</small> cluster units and cationic organic ligands derived from triethylenediamine (Ted). Structural analysis revealed distinct bridging modes of iodide anions within the [Cu<small>₅</small>I<small>₇</small>]<small>²⁻</small> cluster units. Complex <strong>1</strong> contained a rare μ<small>₅</small>-bridging iodide that enhanced the structural rigidity for the [Cu<small>₅</small>I<small>₇</small>]<small>²⁻</small> unit, which should correlate with its superior photoluminescence quantum yield (72.8%) and improved thermal stability compared to complex <strong>2</strong>. Under X-ray excitation, <strong>1</strong> achieved a light yield of 19 010 photons per MeV, surpassing that of the commercial scintillator Bi<small>₄</small>Ge<small>₃</small>O<small>₁₂</small> (BGO, 10 000 photons per MeV), along with a detection limit of 88.5 nGy s<small>⁻¹</small>, well below the typical medical imaging threshold. When incorporated into a flexible polydimethylsiloxane film, <strong>1</strong> achieved a spatial resolution of 8 lp mm<small>⁻¹</small> in X-ray imaging. These results highlight the potential of structurally tailored copper(<small>I</small>) iodide complexes as efficient and cost-effective scintillators for advanced X-ray imaging applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3892-3897"},"PeriodicalIF":2.4,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336613","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":"Brittle or plastic? Revisiting the mechanical behavior of benzoic acid crystals","authors":"Deepak Rajput and Sameer V. Dalvi","doi":"10.1039/D6CE00164E","DOIUrl":"https://doi.org/10.1039/D6CE00164E","url":null,"abstract":"<p >Understanding the mechanical behaviour of organic molecular crystals is essential for their reliable handling, processing, and performance in solid-state applications. Benzoic acid crystals have been reported to be brittle in previous studies. However, in this work, the benzoic acid crystals grown using slow evaporation and sublimation processes exhibited plastic bending upon the application of force on a wider (001) crystallographic face. Single-crystal X-ray diffraction analysis and pairwise interaction energy calculations revealed the presence of a slip plane along the (001) direction, which was formed mainly due to the herringbone packing arrangement of the benzoic acid molecules and a weak edge-to-edge aromatic interaction. A low-energy (001) slip plane with an interlayer separation of approximately 0.896 Å facilitates the plastic deformation of benzoic acid crystals. Nanoindentation analysis of the (001) face yielded elastic modulus (<em>E</em>) and hardness (<em>H</em>) values of 4.26 ± 0.68 GPa and 128.03 ± 38 MPa, respectively, which fall within the range of values reported for plastic organic crystals.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 25","pages":" 3874-3883"},"PeriodicalIF":2.4,"publicationDate":"2026-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336611","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}