Crystal Growth & Design最新文献

{"title":"Substituent-Engineered Multi-Stimuli-Responsive Schiff Base Crystals: from Proton Transfer Mechanisms to Smart Device Prototypes","authors":"Huanfa Feng,&nbsp;, ,&nbsp;Pengpeng Yang,&nbsp;, ,&nbsp;Jinqiu Fu,&nbsp;, ,&nbsp;Mingyu Qin,&nbsp;, and ,&nbsp;Keke Zhang*,&nbsp;","doi":"10.1021/acs.cgd.5c01046","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01046","url":null,"abstract":"<p >The demand for multifunctional, stimuli-responsive crystalline materials capable of stable, rapid, and diverse responses is critical for smart sensing, actuation, and optoelectronics, yet remains challenging in single-component systems. Using substituent replacement in crystal engineering, we modulated crystal packing density to balance ESIPT efficiency, yielding three Schiff base derivatives. In this study, compound B manifests concurrent photochromism and intrinsic elastoplasticity, demonstrating dual photoresponsive behavior. Compound C exhibits robust thermochromism coupled with spontaneous crystal jumping at elevated temperatures. Compound Bu-C displays thermochromism with high-temperature fluorescence quenching while undergoing exceptional, phototriggered explosive decomposition. We establish structure–property relationships linking molecular design to photochromism, thermochromism, mechanoresponse, and photothermal sensing. Mechanistic studies confirm proton-transfer tautomerism underpins photo/thermochromism, while lattice stress release enables mechanoresponse. Leveraging the crystal’s thermochromism, photochromism, and temperature-dependent fluorescence, we demonstrate a photoregulated thermal switch and a multistage anticounterfeiting technology. This work provides novel design principles for advanced multiresponsive crystals, significantly expanding their potential in actuators, sensors, and optoelectronic systems beyond single-function materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8203–8216"},"PeriodicalIF":3.4,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195723","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":"Structural Insights into Luminescent Zn(II) Materials for Picric Acid Detection","authors":"Manik Das,&nbsp;, ,&nbsp;Uttam Kumar Das,&nbsp;, ,&nbsp;Shobhan Aich,&nbsp;, ,&nbsp;Raju Biswas,&nbsp;, ,&nbsp;Soumik Laha,&nbsp;, ,&nbsp;Bidhan Chandra Samanta,&nbsp;, ,&nbsp;Tithi Maity*,&nbsp;, ,&nbsp;Asim Bhaumik*,&nbsp;, and ,&nbsp;Dilip Kumar Maiti*,&nbsp;","doi":"10.1021/acs.cgd.5c00611","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00611","url":null,"abstract":"<p >One luminescent octanuclear porous Zn(II) complex, C1, and another luminescent Zn(II) coordination polymer, C2, have been synthesized by using a salen-type Schiff base ligand H₂L and terephthalic acid (H₂BDC). C1 exhibits a unique single-molecule porous structure, comprising eight Zn(II) centers in a distorted square-shaped architecture. In contrast, C2 features two Zn(II) centers with distinct geometries, adding diversity to its structure. This difference in geometry creates an intriguing structural feature in the complex. Both complexes demonstrate exceptional sensing capabilities, enabling swift and selective detection of picric acid (PA) in aqueous and vapor phases. The detection mechanism involves fluorescence quenching, with a nanomolar detection limit. The quenching process occurs through a joint operation of photoinduced electron transfer (PET), fluorescence resonance energy transfer (FRET), intermolecular charge transfer (ICT), and the inner filter effect (IFE) mechanism.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8021–8034"},"PeriodicalIF":3.4,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195706","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":"Illustrating Extreme Negative Linear Compressibility in Thermosalient Molecular Crystals","authors":"Bruno Mladineo,&nbsp;, ,&nbsp;Teodoro Klaser,&nbsp;, ,&nbsp;Martin Ende,&nbsp;, ,&nbsp;Jasminka Popović,&nbsp;, ,&nbsp;Ivor Lončarić*,&nbsp;, and ,&nbsp;Željko Skoko*,&nbsp;","doi":"10.1021/acs.cgd.5c01043","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c01043","url":null,"abstract":"<p >We report a high-pressure single-crystal X-ray diffraction study of the thermosalient molecular crystal N’-2-propylidene-4hydroxybenzohydrazide. We find that it features one of the largest negative linear compressibilities recorded, with a coefficient of −39 TPa^–1. With increasing pressure, it converts to a positive linear compressibility and at even higher pressures again to a negative linear compressibility. This switchable behavior arises from the pressure-induced straightening of the hydrogen-bonded zigzag chains, which is eventually counteracted by direct bond compression. To capture this mechanism, we trained a machine-learning interatomic potential and performed quasi-harmonic free-energy calculations, thereby obtaining atomistic insight across the whole pressure range. These findings broaden the still-scarce catalog of organic crystals that combine thermosalient activity with experimentally verified, pressure-tunable NLC.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8196–8202"},"PeriodicalIF":3.4,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195673","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":"DFT Insights on the Modulation of Different Bridging Groups for the Optical Properties of Charge-Transfer Cocrystal","authors":"Zhouyu Jiang,&nbsp;, ,&nbsp;Yaqin Chen,&nbsp;, ,&nbsp;Wenhao Su,&nbsp;, ,&nbsp;Zihui Jing,&nbsp;, ,&nbsp;Arshad Khan,&nbsp;, ,&nbsp;Rabia Usman,&nbsp;, and ,&nbsp;Mingliang Wang*,&nbsp;","doi":"10.1021/acs.cgd.5c00397","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00397","url":null,"abstract":"<p >The functional group differences in molecular structure and the self-assembly of cocrystals of multicomponent molecules are two important factors affecting the optical properties of solid-state organic luminescent materials. In this work, three electron-donor anthracene-based molecules with different bridging groups and their charge-transfer cocrystals with electron-acceptor 1,2,4,5-benzenetetracarbonitrile molecule were synthesized and cultured, aiming to explore the influence of donors’ conjugate length and steric hindrance effect on cocrystals’ optical properties. Crystal structure analysis confirmed that the donor’s own crystal structure was a dispersed arrangement, while cocrystals had a unified π···π stacking. Solid-state optical testing indicated that increasing the conjugation length and introducing TCNB could lead to significant red-shifts in the UV absorption band and fluorescence emission peak position of three donors, while significantly increasing the conjugate length of a donor’s bridging group would only lead to slight red-shifts in that of the cocrystals, and the steric hindrance effect of donors had no significant impact on it. The difference was that the fluorescence quantum yields and fluorescence lifetime of three donors and cocrystals all increased significantly with the increase of the steric hindrance effect. Theoretical calculations confirmed that the first excited state processes of the three donors and cocrystals were mainly HOMO→LUMO transitions. Therefore, the LUMO–HOMO gap value determined the energy level difference in the first excited state. Both increasing the conjugation length and introducing TCNB would lead to a reduction in energy level difference, thereby causing a red-shift in the spectra.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"7941–7952"},"PeriodicalIF":3.4,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195726","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 and Ratiometric Fluorescence Tuning of the Eu-Metal Oxide Framework for Formaldehyde Sensing via Photoinduced Electron Transfer","authors":"Yuming Zhao,&nbsp;, ,&nbsp;Dan Yue,&nbsp;, ,&nbsp;Yongpeng Zhu,&nbsp;, ,&nbsp;Rudie Zhang,&nbsp;, ,&nbsp;Tuantian Zhang,&nbsp;, ,&nbsp;Pengju Yin,&nbsp;, ,&nbsp;Bowen Qin,&nbsp;, ,&nbsp;Jinhui Liu*,&nbsp;, ,&nbsp;Zhenling Wang*,&nbsp;, and ,&nbsp;Yu Fu*,&nbsp;","doi":"10.1021/acs.cgd.5c00947","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00947","url":null,"abstract":"<p >Combining the potential advantages of metal–organic frameworks (MOFs) with the distinctive luminescent behavior of lanthanide metal ions, a fluorescence probe (Eu-MOF, Eu-BDC-NH₂) with dual fluorescence emissions of ligand (λ = 431 nm) and Eu³⁺ (λ = 617 nm) is synthesized using a straightforward room-temperature crystal growth process. The obtained Eu-BDC-NH₂ crystal possesses an abundance of uncoordinated amino groups, which serve as effective active sites for the selective recognition of formaldehyde (FA). Owing to the presence of photoinduced electron transfer (PET) between the amino group and the adjacent ligand, the fluorescence of the ligand in the Eu-BDC-NH₂ is turned off. Upon the introduction of FA, the amino group interacts with FA, which inhibits the PET process and simultaneously diminishes the “antenna effect” of sensitizing Eu³⁺. Consequently, the ligand fluorescence is turned on, and the Eu³⁺ fluorescence is weakened, enabling the highly sensitive ratiometric fluorescence detection of FA. Compared with the single emission fluorescence spectrum, Eu-BDC-NH₂ can achieve internal self-calibration by measuring the ratio of fluorescence intensity of the two wavelengths in the system to overcome signal fluctuations and provide more accurate and reliable information. Furthermore, by integrating smartphones, an intelligent sensing system has been developed to enhance the visualization of FA detection, where the fluorescence color visible to the naked eye shifts from red to blue. Specifically, this work utilizes a straightforward dripping method performed at room temperature, which not only simplifies the experimental synthesis process but also adheres to the principles of green chemistry, thereby offering a novel perspective and methodology for the development of MOF-based fluorescence probes.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8147–8156"},"PeriodicalIF":3.4,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195742","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":"Two Isoreticular 2D Zn(II) Coordination Polymers (CPs) Based on a Flexible Tripodal Thioether-Based Pyridyl Ligand and Two V-Shaped Dicarboxylate Ligands: Structural Characterization, CO2 Uptakes, and Water Ad-/Desorption Isotherms","authors":"Yu-Chen Chung,&nbsp;, ,&nbsp;Hsin-Fang Chang,&nbsp;, ,&nbsp;Yu-Hsuan Hou,&nbsp;, ,&nbsp;Chih-Chieh Wang*,&nbsp;, ,&nbsp;Shih-I Lu*,&nbsp;, ,&nbsp;Gene-Hsiang Lee,&nbsp;, ,&nbsp;Su-Ying Chien,&nbsp;, ,&nbsp;Bo-Hao Chen,&nbsp;, and ,&nbsp;Yu-Chun Chuang*,&nbsp;","doi":"10.1021/acs.cgd.5c00431","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00431","url":null,"abstract":"<p >Two Zn-based mixed-ligand coordination polymers (CPs) constructed by a tripodal thioether-based pyridyl ligand, 1,3,5-tris(4-pyridylsulfanylmethyl)-2,4,6-trimethylbenzene (L¹), and two V-shaped 5-R-1,3-isophthalate ligands, {[Zn(L¹)(5-nipa)]·C₂H₅OH·H₂O}_∞ (<b>1</b>) and {[Zn(L¹)(5-bipa)]·2C₂H₅OH·H₂O}_∞ (<b>2</b>) (5-nipa^2– = dianion of 5-nitroisophthalic acid, and 5-bipa^2– = dianion of 5-bromoisophthalic acid), have been synthesized and structurally characterized. CPs <b>1</b> and <b>2</b> are isoreticular, in which L¹ acts as a bridging ligand with a <i>bis</i>-monodentate coordination mode in a <i>cis–cis–cis</i> structural configuration, connecting the Zn(II) ions to form a 1D helical chain. Two helical chains are entwined together to generate a 1D double-helical chain, and neighboring double-helical chains are interlinked via the connectivity between Zn(II) ions and 5-nipa^2– in <b>1</b> and 5-bipa^2– in <b>2</b> with <i>bis</i>-monodentate coordination modes and arranged orderly in an ABAB··· manner to create 2D layered-like CPs. Adjacent 2D layers are then assembled in an ABAB··· fashion to fulfill their 3D supramolecular networks. Compounds <b>1</b> and <b>2</b> displayed reversible solvent (H₂O, MeOH, and EtOH) de-/adsroption behaviors by cyclic de-/resolvation TG analyses. Significant CO₂ sorption occurs at 195 K for pretreated <b>1</b>′ and <b>2</b>′, indicating that structural transformation happens to accumulate the adsorbed CO₂ molecules. Water vapor adsorption/desorption isotherms for pretreated <b>1</b>′ and <b>2</b>′ show maximum values of 59.54 cm³ g^–1 at a relative pressure <i>P</i>/<i>P</i>₀ of 1.02 for <b>1</b>′ and 91.37 cm³ g^–1 at a relative pressure <i>P</i>/<i>P</i>₀ of 1.01 for <b>2</b>′, corresponding to adsorption of approximately two and three water molecules per asymmetric unit (ASU).</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"7953–7965"},"PeriodicalIF":3.4,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195715","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":"Quantifying Packing Efficiency in Molecular Crystals: A Close Packing Index Based on Hirshfeld Surfaces","authors":"Rahul Dahiya,&nbsp;, ,&nbsp;Soyal Sabu,&nbsp;, ,&nbsp;Srijan Mondal,&nbsp;, and ,&nbsp;Sajesh P. Thomas*,&nbsp;","doi":"10.1021/acs.cgd.5c00814","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00814","url":null,"abstract":"<p >The degree of close packing in molecular crystals can dictate their mechanical, chemical, and photophysical properties. Here, we present a simple descriptor of close packing in molecular crystals, based on Spackman’s intermolecular boundary surfaces, known as Hirshfeld surfaces. In comparison to Kitaigorodskii’s packing index (KPI), the values of this close packing index (CP_i) offer a more accurate description of packing efficiency and demonstrate stronger correlations with properties such as melting point and lattice cohesive energy examined in two different series of crystal structures in this study. The usefulness of this CP_i is demonstrated here for comparing multi-component cocrystals, high <i>Z</i>′ structures, and isostructural molecular crystals of chemical analogs, for which the direct comparison of crystal density would be less meaningful. Correlations of the CP_i values with the lattice cohesive energies, melting points, and mechanical properties such as Young’s moduli have been examined. These results imply that CP_i may serve as a simple yet useful structural tool in crystal engineering studies.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8081–8088"},"PeriodicalIF":3.4,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195678","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":"Robust Microporous Naphthalenediimide-Based Hydrogen-Bonded Organic Framework for High-Performance Lithium-Ion Storage","authors":"Qiling Li,&nbsp;, ,&nbsp;Yuxiang Zhao,&nbsp;, ,&nbsp;Xianfu Shen,&nbsp;, ,&nbsp;Shu-Biao Xia*,&nbsp;, and ,&nbsp;Jian-Jun Liu*,&nbsp;","doi":"10.1021/acs.cgd.5c00582","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00582","url":null,"abstract":"<p >Hydrogen-bonded organic frameworks (HOFs) have attracted extensive attention in recent years due to their advantages of large surface area, high crystallinity, and high porosity. Unfortunately, their application in lithium-ion storage remains difficult to achieve because hydrogen bonds are prone to dissociation in the electrolyte, which degrades the integrity of the structure. This problem can be overcome with a naphthalenediimide-based HOF (<b>NDI-HOF</b>), designed and synthesized using the building block <i>N</i>,<i>N</i>′-bis[(1-oxidopyridin-1-ium-4-yl)methyl]-1,8:4,5-naphthalene tetracarboxdiimide (DPNDI-2O). The multisite hydrogen bonds and π–π interactions regulated by the DPNDI-2O molecule endow this material with unique chemical and thermal stability. It has a very low solubility in most nonpolar and polar organic solvents and can maintain its crystallinity, thus enabling its electrochemical application. This stable HOF material shows a high capacity and outstanding cycling stability for Li⁺ ion storage. The material retained a specific capacity of 225 mAh·g^–1 over 1000 cycles at a 400 mA·g^–1 current density. This enhanced capacity and outstanding cycle life stem from the synergistic combination of numerous active sites and structural robustness. It maintained a specific capacity of 225 mAh·g^–1 after 1000 cycles at 400 mA·g^–1. The enhanced specific capacity and superior cycling performance originate from the synergistic interplay between the abundant active sites and the robust structure. Molecular simulations identified Li⁺ ion binding locations in the material structure and suggested that intermolecular diffusion occurs with a comparatively low energy barrier.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8002–8009"},"PeriodicalIF":3.4,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195699","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":"Modulator Driven Formation of a Very Complex Self-Catenated Zinc Metal–Organic Framework","authors":"Alan Braschinsky,&nbsp;, ,&nbsp;Davide M. Proserpio,&nbsp;, ,&nbsp;Toby J. Blundell,&nbsp;, ,&nbsp;Eduardo Rezende Triboni,&nbsp;, and ,&nbsp;Jonathan W. Steed*,&nbsp;","doi":"10.1021/acs.cgd.5c00992","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00992","url":null,"abstract":"<p >Solvothermal reaction of <i>N</i>,<i>N</i>′-bis(5-isophthalic acid)naphthalenediimide (H₄BINDI) with zinc(II) nitrate hexahydrate in dimethylformamide (DMF) in the presence of trifluoroacetic acid as a modulator gives rise to a self-catenated Metal–organic framework (MOF) termed BINDI-ZnSC of unprecedented topological complexity. Using the “all node” method, the topology is assigned as a six-nodal net with point symbol {4.10²}₂{4.12²}{4.6.8}{4².6.8.10⁶}{6.10²}. In contrast to interpenetrated and other self-catenated MOFs that often exhibit limited pore volume, BINDI-ZnSC exhibits a total of 3730 ų (62.5% of the unit cell) of solvent-filled channels per unit cell, suggesting that the material is potentially capable of encapsulating not only single molecules but also molecular clusters of some small molecules.</p><p >A self-catenated MOF of unprecedented topological complexity exhibits a 6-nodal net with point symbol {4.10²}₂{4.12²}{4.6.8}{4².6.8.10⁶}{6.10²}. In contrast to interpenetrated and other self-catenated MOFs that often exhibit limited pore volume, 62.5% of the structure comprises solvent-filled channels.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8181–8187"},"PeriodicalIF":3.4,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.5c00992","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195700","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":"Photomechanical Anthracenophane Crystals: Theory, Experiment, and Composite Actuator Performance","authors":"Kevin Lam,&nbsp;, ,&nbsp;Pedro Molina-Portillo,&nbsp;, ,&nbsp;Veronica Carta,&nbsp;, ,&nbsp;Tomohiko Nishiuchi,&nbsp;, ,&nbsp;Matthew Ticknor,&nbsp;, ,&nbsp;Ryan C. Hayward,&nbsp;, ,&nbsp;Rabih O. Al-Kaysi,&nbsp;, ,&nbsp;Takashi Kubo,&nbsp;, ,&nbsp;Gregory J. O. Beran*,&nbsp;, and ,&nbsp;Christopher J. Bardeen*,&nbsp;","doi":"10.1021/acs.cgd.5c00851","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00851","url":null,"abstract":"<p >The anthracene [4 + 4] photocycloaddition is a negative photochromic reaction utilized in photomechanical materials. In crystals, this reaction requires that monomeric anthracene rings adopt a face-to-face packing motif. Anthracenophane derivatives preorganize covalently attached anthracenes for an intramolecular [4 + 4] photocycloaddition reaction, decoupling the photochemistry from the crystal packing. In this work, three anthracenophanes, bi(anthracene-9,10-dimethylene) (<b>1</b>), (-H)monobenzoannulated [2.2](9,10)anthracenophane (<b>2</b>) and (-OEt)monobenzoannulated [2.2](9,10)anthracenophane (<b>3)</b>, are assessed as potential solid-state photomechanical materials. Crystal structures of the reactant and photoproduct forms are obtained, and all crystals exhibit photosalient behavior. Although all three molecules rely on the same photochemistry, theoretical analysis predicts widely varying photomechanical work outputs among these derivatives and their polymorphs, with neat crystals of <b>2</b> predicted to exhibit a work density of up to 68 MJ/m³ due to the favorable alignment of the anthracene ring distortions. Enhanced thermal reversibility is observed for <b>2</b> and <b>3</b> due to a 60% reduction in the activation energy for photodimer dissociation, leading to recovery of the reactant within minutes at room temperature. The more soluble <b>3</b> could be incorporated into a composite ceramic-organic bending actuator that showed good reversibility, although its estimated work density of 2.6 × 10³ J/m³ is several orders of magnitude less than that predicted theoretically for the neat crystal. This large discrepancy suggests that improved processing and actuator design will be required to approach the theoretical limits of these photomechanical crystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 19","pages":"8089–8099"},"PeriodicalIF":3.4,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195592","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}