Crystal Growth & Design最新文献

{"title":"Structural Insights into the Resveratrol-Piperazine Cocrystal Forms Enabling the Cocrystallization Process Development from Solution","authors":"Doriana Timeea Ungur,&nbsp;Coca Angela Iordache,&nbsp;Claudia Anamaria Brăilă,&nbsp;Delia Anca Pop,&nbsp;Monica Cristina David,&nbsp;Jeanina Pandele-Cuşu,&nbsp;Victor Fruth,&nbsp;Ingemar Pongratz,&nbsp;Bogdan-Cezar Iacob,&nbsp;Ede Bodoki and Mihaela Maria Pop*,&nbsp;","doi":"10.1021/acs.cgd.4c0111310.1021/acs.cgd.4c01113","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01113https://doi.org/10.1021/acs.cgd.4c01113","url":null,"abstract":"<p >The aim of this study was to structurally characterize resveratrol-piperazine cocrystal forms using the single-crystal X-ray diffraction technique. Two resveratrol-piperazine cocrystals, designated solvent-free form (RP1) and tetrahydrofuran solvated form (RP2), were successfully synthesized with a solvent-based method. The crystal structure of the anhydrate cocrystal is similar to the non-disordered structure reported in the literature, but it exhibits a disordered piperazine molecule. Notably, this disorder leads to small variations in the unit cell parameters compared to the non-disordered structure, thus generating a distinct crystal structure as such. Nevertheless, this new, disordered structure identified in the single crystal is an intermediate form that readily transforms into the non-disordered structure upon mechanical processing. The non-disordered anhydrate is stable upon storage at elevated temperature and relative humidity, while the solvate is unstable under the same accelerated conditions and transforms into the anhydrate cocrystal. Additionally, the solvent molecules are not bonded in the solvated crystal structure and thus desolvation is readily achieved via slurry at elevated temperatures in an antisolvent. This desolvation behavior makes the solvated cocrystal a suitable intermediate for producing the more stable anhydrate cocrystal. To summarize, this study provides a comprehensive understanding of the resveratrol-piperazine cocrystallization process by revealing the detailed structural characteristics of the cocrystal forms. Furthermore, it provides a proof of concept for developing a solution cocrystallization process able to achieve resveratrol purification and simultaneously provide a cocrystal product with enhanced aqueous solubility.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1330–1343 1330–1343"},"PeriodicalIF":3.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547488","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":"Crystal Growth & Design at 25: Still Building and Serving the Solid State Research Communities","authors":"Robin D. Rogers*,&nbsp; and ,&nbsp;Allan S. Myerson,&nbsp;","doi":"10.1021/acs.cgd.5c0002310.1021/acs.cgd.5c00023","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00023https://doi.org/10.1021/acs.cgd.5c00023","url":null,"abstract":"","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 4","pages":"874–877 874–877"},"PeriodicalIF":3.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435969","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":"Architectonic and Desolvation Activation Energies of Five New Mixed-Ligand Copper(II) Coordination Polymers of 5-Sulfoisophthalate and 1,3-Bis(1H-imidazol-1-yl)propane or 1,4-Bis(1H-imidazol-1-yl)butane","authors":"Valoise Brenda Nguepmeni Eloundou,&nbsp;Patrice Kenfack Tsobnang*,&nbsp;Theophile Kamgaing and Susan A. Bourne*,&nbsp;","doi":"10.1021/acs.cgd.4c0167110.1021/acs.cgd.4c01671","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01671https://doi.org/10.1021/acs.cgd.4c01671","url":null,"abstract":"<p >Five new coordination polymers, [Cu₃(imp)₄(sip)₂]•2H₂O <b>(1)</b>, {[Cu₃(imp)₆(H₂O)_2.5](sip)₂}•15H₂O <b>(2)</b>, [Cu₂(imp)(sip)(OH)(CH₃OH)]•CH₃OH <b>(3)</b>, {[Cu₃(timp)₆(H₂O)₄](sip)₂}•15H₂O <b>(4)</b>, and [Cu₃ (timp)₃(sip)₂(H₂O)₂]•4H₂O <b>(5)</b> were synthesized via solvothermal reactions using copper(II) and mixed ligands, including 5-sulfoisophthalate ions, (sip) 1,3-bis(1H-imidazol-1-yl)propane (imp), and 1,4-bis(1H-imidazol-1-yl)butane (timp). Characterization techniques, including FT-IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction, confirmed the successful formation of these polymers. Single-crystal X-ray diffraction revealed that compounds <b>1</b>, <b>4</b>, and <b>5</b> crystallize in space group <i></i><math><mi>P</mi><mover><mrow><mn>1</mn></mrow><mrow><mo>¯</mo></mrow></mover></math>, while <b>2</b> and <b>3</b> crystallize in <i>P</i>2₁/<i>c</i> and <i>Pnnm,</i> respectively. All of the coordination polymers include multiple copper ions with different coordination geometries. In compounds <b>1</b>, <b>2</b>, <b>3</b>, and <b>4,</b> the copper(II) ions have octahedral and trigonal bipyramidal geometries, whereas <b>5</b> contains copper(II) ions with square pyramidal and square planar geometries. The thermal behavior of all compounds was investigated under a nitrogen atmosphere. Decomposition occurs within the 150–300 °C range, beginning with desolvation. The activation energies for this process were measured, ranging from 32 to 89 kJ mol–¹, providing valuable insights into the compounds’ thermal properties. Notably, desolvation studies indicated similar thermal properties for <b>1</b>, <b>3</b>, and <b>5</b>, which exhibit single-step desolvation, while <b>2</b> and <b>4</b> dehydrate in two distinct steps.</p><p >The ability of 5-sulfoisophthalic acid and bisimidazole derivatives to build 2D- and 3D-mixed ligand coordination polymers is shown in this work. The five compounds reported are obtained from the same reagents but different solvents.Thermal analysis and desolvation kinetic studies of the five compounds show their promising application in dehumidification.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1575–1587 1575–1587"},"PeriodicalIF":3.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01671","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547548","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":"In Situ Monitoring of Copper Benzenehexathiol Coordination Polymer Formation via High-Resolution Liquid-Cell Transmission Electron Microscopy","authors":"David Mücke*,&nbsp;Zhiyong Wang,&nbsp;Xinliang Feng and Ute Kaiser*,&nbsp;","doi":"10.1021/acs.cgd.4c0171410.1021/acs.cgd.4c01714","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01714https://doi.org/10.1021/acs.cgd.4c01714","url":null,"abstract":"<p >Liquid-cell transmission electron microscopy (LC-TEM) represents a promising technique for obtaining detailed knowledge about crystal nucleation and growth. For conjugated coordination polymer (c-CP) crystals, which are constructed by linking conjugated organic ligands with metal nodes, the growth mechanism remains poorly understood, making LC-TEM an ideal method to fill this gap. However, the general low stability of these materials under the electron beam has hindered high-resolution experiments. Here, we overcome this obstacle and demonstrate high-resolution LC-TEM experiments for the growth of a copper-linked benzenehexathiol (BHT) c-CP. Surprisingly, the synthesis led to the formation of Cu₄(BHT) instead of the expected Cu₃(BHT), which is found in corresponding <i>ex-situ</i> experiments. We attribute the formation of different structures in <i>ex-situ</i> and <i>in situ</i> experiments to radiolysis occurring during the interaction of the electron beam with the solutions inside the liquid cell, as well as the restrictions dictated by the laminar flow in the microfluidic system.</p><p >Liquid-cell transmission electron microscopy (LC-TEM) high-resolution imaging of conjugated coordination polymer (c-CP) crystal growth is demonstrated, despite the low stability of these polymers under the electron beam. Copper-linked benzenehexathiol (BHT) c-CP unexpectedly forms Cu₄(BHT) instead of Cu₃(BHT), attributed to radiolysis-induced reduction of the copper source.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1622–1627 1622–1627"},"PeriodicalIF":3.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01714","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547542","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":"Ternary Phase Behavior of 1,3-Dipalmitoyl-2-linoleoylglycerol (PLP), 1-Palmitoyl-2-linoleoyl-3-stearoyl-rac-glycerol (PLS), and 1,3-Distearoyl-2-linoleoylglycerol (SLS): Minor TAG Species of Vegetable Fats and Oils","authors":"Katsiaryna Kalenchak*,&nbsp;Markéta Berčíková,&nbsp;Kateřina Sasínová,&nbsp;Tereza Honzíková,&nbsp;Radek Beneš,&nbsp;Jan Rohlíček,&nbsp;Jan Kyselka and Vladimír Filip,&nbsp;","doi":"10.1021/acs.cgd.4c0130810.1021/acs.cgd.4c01308","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01308https://doi.org/10.1021/acs.cgd.4c01308","url":null,"abstract":"<p >The focus on healthier alternatives has brought about the need to study the physical properties of fats more thoroughly. Currently, the major aim is to develop systems that bring the desired physical properties to the final products and, ideally, can additionally enhance their health benefits for consumers. Research often begins with understanding the behavior of single TAG molecules and gradually moves toward multicomponent systems. In our study, the phase behavior of three minor triacylglycerols of cocoa butter was determined. The synthesized 1,3-dipalmitoyl-2-linoleoylglycerol, 1-palmitoyl-2-linoleoyl-3-stearoyl-<i>rac</i>-glycerol, and 1,3-distearoyl-2-linoleoylglycerol as well as their binary and ternary mixtures were analyzed during rapid cooling at 30 °C·min^–1 and heating at 2 °C·min^–1 using X-ray powder diffraction and differential scanning calorimetry. Based on the data obtained, we proposed state diagrams for the binary and ternary mixtures, which could be valuable for modeling fat structuring systems in food and cosmetic applications. These findings offer deeper insight into the crystallization behavior of fats, addressing complex phenomena of cocoa butter crystallization.</p><p >This study investigates the phase behavior of PLP, PLS, and SLS─minor triacylglycerols found in vegetable fats and oils, particularly in cocoa butter. Binary and ternary mixtures were analyzed using DSC and XRPD. The constructed state diagrams revealed eutectic formations, providing insight into crystallization behavior in multicomponent lipid systems.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1372–1385 1372–1385"},"PeriodicalIF":3.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01308","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547476","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":"Construction of Symmetric Energetic Compounds with Lower Sensitivity via Integration of Flexible Chains","authors":"Meiqi Xu,&nbsp;Wen-Shuai Dong,&nbsp;Zu-jia Lu,&nbsp;Qamar-un-Nisa Tariq,&nbsp;Zhimin Li,&nbsp;Qiyao Yu* and Jian-Guo Zhang*,&nbsp;","doi":"10.1021/acs.cgd.4c0121710.1021/acs.cgd.4c01217","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01217https://doi.org/10.1021/acs.cgd.4c01217","url":null,"abstract":"<p >High-energy-density materials (HEDMs) have made significant progress in defense and space applications, but they still confront the challenges of unsatisfactory safety, sensitivity, and chemical applicability. In this work, a strategy to synthesize symmetric energetic materials by introducing flexible chains (−CH₂– or −CH₂CH₂−) is reported based on 5-azido-3-nitro-1<i>H</i>-1,2,4-triazole <b>1</b>. <i>N</i>,<i>N</i>′-Methylene bridged compound <b>2</b> and <i>N</i>,<i>N</i>′-ethylene bridged compound <b>3</b> are successfully obtained through a one-step synthesis with high yield. The introduction of flexible chains significantly reduced the mechanical sensitivity of the two compounds. This change can be attributed to the synergistic effects of several factors, including the formation of hydrogen bonds, reduced oxygen balance, and variations in the ESP of the molecular surface. As a result, the bridged compound <b>2</b> (IS = 15 J, FS = 360 N) and compound <b>3</b> (IS &gt; 40 J, FS &gt; 360 N) exhibit lower sensitivity compared to the monocyclic functional integrated compound <b>1</b> (IS = 5 J, FS &gt; 42 N). The detonation velocities of compounds <b>2</b> and <b>3</b> are 8439 and 7979 m·s^–1, respectively.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1355–1363 1355–1363"},"PeriodicalIF":3.2,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547121","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":"Coordination Polymers As Catalysts in Knoevenagel Condensations─A Critical Review Analysis under Synthesis Conditions and Green Chemistry","authors":"Luca Dias Tavares Louzada,&nbsp;Pedro Netto Batalha and Filipe Barra de Almeida*,&nbsp;","doi":"10.1021/acs.cgd.5c0003310.1021/acs.cgd.5c00033","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00033https://doi.org/10.1021/acs.cgd.5c00033","url":null,"abstract":"<p >Knoevenagel condensation is an important reaction where C–C double bonds can be formed by reacting carbonyl with active methylene compounds. For materials and pharmaceutical chemistry, this reaction plays an important role in the search for new products for which an effective catalyst is fundamental. Due to its high activity, selectivity, and facile recovery, coordination polymers stand as an important heterogeneous catalyst for Knoevenagel condensation. This review builds an extensive analysis correlation between synthesis conditions and coordination polymer properties as catalysts. The pivotal correlation between solvent properties (protic/aprotic), reaction conditions, and the influence of coordination polymer dimensionality on the reaction selectivity is thoroughly examined. The mono/bifunctional catalyst characteristic is also highlighted, with an in-depth examination of the reaction mechanism to clarify the contribution of Lewis acid and basic sites. Further, the reaction under environmentally friendly conditions was identified among all of the reactions to determine the greenest catalyst. In this perspective, this perspective establishes a robust foundation for the future design and application of coordination polymers as catalysts in Knoevenagel condensation.</p><p >In this review, an extensive analysis of texts exploring the application of coordination polymers (CPs) in Knoevenagel condensation (KC) is carried out. The primary focus is on unraveling the intricate relationship between catalytic potential and properties of CPs, emphasizing the reaction conditions, mechanism and their potential to facilitate the KC, highlighting works on which the reactions were conducted under green conditions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1708–1723 1708–1723"},"PeriodicalIF":3.2,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547195","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":"Crystal Structure of ZSM-48: A 40 Year-Old Puzzle Resolved","authors":"Lynne B. McCusker*,&nbsp;Bernd Marler,&nbsp;Christian Baerlocher,&nbsp;Youngkyu Park and Hermann Gies,&nbsp;","doi":"10.1021/acs.cgd.4c0169210.1021/acs.cgd.4c01692","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01692https://doi.org/10.1021/acs.cgd.4c01692","url":null,"abstract":"<p >Eight calcined ZSM-48-type materials, selected for their diversity, have been examined crystallographically to determine whether they can be described in the same way as can RUB-58 (framework type <b>RFE</b>), with blocks of a single framework structure separated by shear planes. In RUB-58, only one framework structure is present, but it can adopt either of two origins related by exactly one-half of a unit cell along the channel direction. The framework blocks can connect to one another seamlessly along well-defined shear planes. The eight materials were synthesized in two different laboratories using seven different organic structure-directing agents under a variety of conditions. At first glance, their diffraction patterns are similar, but the reflection intensities and peak shapes differ. Analysis of the eight structures revealed that indeed all can be refined using the RUB-58 structural model. Only the amount of the shifted framework and the peak widths (arising primarily from different crystallite sizes) differ. Comparison of the diffraction patterns generated from several series of disorder models (using two polymorphs) with the measured ones shows that those from the RUB-58 single-framework model yield the best matches. Geometric optimization, simulations of different shear planes and the morphology suggest that the shear plane along (110) is the most likely one. These results indicate that the disorder (involving different polymorphs), which has been assumed for ZSM-48-type materials for nearly 40 years, probably does not exist.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1605–1613 1605–1613"},"PeriodicalIF":3.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547193","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":"Mechanism of Heteroepitaxial Growth of Boron Carbide on the Si-Face of 4H-SiC","authors":"Yamina Benamra,&nbsp;Laurent Auvray,&nbsp;Jérôme Andrieux,&nbsp;François Cauwet,&nbsp;Marina Gutierrez,&nbsp;Fernando Lloret,&nbsp;Daniel Araujo,&nbsp;Romain Bachelet,&nbsp;Bruno Canut and Gabriel Ferro*,&nbsp;","doi":"10.1021/acs.cgd.4c0160110.1021/acs.cgd.4c01601","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01601https://doi.org/10.1021/acs.cgd.4c01601","url":null,"abstract":"<p >Heteroepitaxial boron carbide (B_<i>x</i>C) can be grown on the Si face of 4H-SiC(0001) using a two-step process involving substrate boridation at 1200 °C under BCl₃ + H₂, followed by a chemical vapor deposition (CVD) growth step at 1600 °C by adding a C₃H₈ precursor. However, an in-depth investigation of the early growth stages revealed that complex reactions occur before starting the CVD at high temperature. Indeed, after boridation, the 35 nm B_<i>x</i>C buffer layer is covered by an amorphous B-containing layer, which evolves and reacts during the temperature ramp-up between 1200 and 1600 °C. Despite the formation of new phases (Si, SiB₆), which could be explained by significant solid-state diffusion of Si, C, and B elements through the thin B_<i>x</i>C layer, the CVD epitaxial regrowth upon reaching 1600 °C does not seem to be affected by these phases. The resulting single-crystalline B_<i>x</i>C layers display the epitaxial relationship [101̅0]B_<i>x</i>C(0001)∥[101̅0]4H-SiC(0001). The layers exhibit a B₄C composition, e.g., the highest possible C content for the B_<i>x</i>C solid solution.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1506–1513 1506–1513"},"PeriodicalIF":3.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547181","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":"Effect of Mechanical Properties and Photoluminescence in Elastic Crystals Triggered by Substituent Regioisomerism","authors":"Qiang Zhao,&nbsp;Dongqing Lin,&nbsp;Xun Fu,&nbsp;Lizhu Dong,&nbsp;Yugang Chen,&nbsp;Jinyi Lin,&nbsp;Chuanxin Wei*,&nbsp;Man Xu*,&nbsp;Jianfeng Zhao and Linghai Xie*,&nbsp;","doi":"10.1021/acs.cgd.4c0155210.1021/acs.cgd.4c01552","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01552https://doi.org/10.1021/acs.cgd.4c01552","url":null,"abstract":"<p >Deformable organic photoluminescent crystals are a kind of fundamental material to exploit cutting-edge flexible optoelectronic devices. However, the realization that modulation of mechanical and photoluminescent properties is difficult due to structural properties, relationships for bendable molecular crystals remain unclear, especially between molecular packing, mechanical properties, and photoluminescence (PL). Herein, we report different supramolecular structures of intermolecular π···π stacking via the substituent regioisomerism effect (SRIE), based on three crystalline dicarbazol-9-yl-based pyrazine regioisomers of para-, meta-, and ortho-convergent substitutions (<i>p</i>-DCzP, <i>m</i>-DCzP, and <i>o</i>-DCzP, respectively). We discover that the elasticity of <i>p</i>-DCzP and <i>m</i>-DCzP crystals benefit from one-dimensional π···π stacking chains of carbazole (Cz) units, while the brittleness of <i>o</i>-DCzP crystals results from the multidirectional π···π stacking of Cz units. Molecular dynamics (MD) simulations suggest that the energy of one-dimensional π···π stacking supramolecular chains is beneficial for reducing noncovalent interaction energy and stabilizing the aggregation structures. In addition, such π···π stacking chains in elastic crystals of <i>m</i>-DCzP can vanish the aggregation-caused quenching effect to maintain higher photoluminescence quantum yields of blue emission from dilute solutions to crystals. This research reveals the SRIE on mechanical properties and photoluminescence in molecular crystals. We believe that this work will provide new perspectives for the development of flexible optoelectronic functional crystal materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1448–1456 1448–1456"},"PeriodicalIF":3.2,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547310","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}