Crystal Growth & Design最新文献

{"title":"Solvatomorphs of the Dapsone Structurally Related Molecule 3,3′-Diaminodiphenyl Sulfone with Class 2 Residual Solvents: Insights into Their Crystal Structures, Stability, and Transformations","authors":"Martina Lippi,&nbsp;Meriem Goudjil,&nbsp;Patrizia Rossi*,&nbsp;Jacopo Ceccarelli,&nbsp;Samuele Ciattini and Paola Paoli,&nbsp;","doi":"10.1021/acs.cgd.4c0093810.1021/acs.cgd.4c00938","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00938https://doi.org/10.1021/acs.cgd.4c00938","url":null,"abstract":"<p >Three new solvates of 3,3′-diaminodiphenyl sulfone (<b>3APS·ACN_m</b>, <b>3APS·DX_m</b>, and <b>3APS·2DX_o)</b> and their solid-state analyses are reported. The two monosolvate compounds (<b>3APS·ACN_m</b> and <b>3APS·DX_m</b>) may be obtained in the pure form by using different synthetic strategies (e.g., slow evaporation of the solvent, slurry, or adsorption of the solvent), while the disolvate one (<b>3APS·2DX_o</b>) was always obtained in the mixture form with <b>3APS·DX_m</b>. Interestingly, a previously reported acetonitrile solvate (<b>3APS·ACN_o</b>) was never obtained during the different synthesis attempts. The stability (varying times and temperatures) of the investigated compounds and a preliminary selective adsorption test are also reported. An <i>in silico</i> analysis of the two solvatomorphs with acetonitrile (ACN) and the two different 1,4-dioxane (DX) solvates provides hints to rationalize the results of the solid-state behavior investigation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 23","pages":"9896–9908 9896–9908"},"PeriodicalIF":3.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761073","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":"Neutron Vibrational Spectroscopic Study of the Acetonitrile:Acetylene (1:2) Cocrystal Relevant to Titan, Saturn’s Moon","authors":"Morgan J. Kramer,&nbsp;Luke L. Daemen,&nbsp;Yongqiang Cheng,&nbsp;Rafael Balderas-Xicohtencatl,&nbsp;Anibal J. Ramirez-Cuesta,&nbsp;Craig M. Brown and Tomče Runčevski*,&nbsp;","doi":"10.1021/acs.cgd.4c0105010.1021/acs.cgd.4c01050","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01050https://doi.org/10.1021/acs.cgd.4c01050","url":null,"abstract":"<p >Saturn’s moon Titan features a surface composed of various organic solids with pronounced compositional and structural diversity. On top of the icy core, the surface experiences a temperature of ≈93 K and pressure of ≈1.45 atm. Under these conditions, most small organic molecules exist as solids and form Titanean minerals. Acetonitrile and acetylene are two of these molecules, which can form single-component molecular solids and also a 1:2 binary cocrystal. Here, we present a combined neutron vibrational spectroscopic study, neutron powder diffraction study, and theoretical modeling of the cocrystal and corresponding single-phase solids. This combined study resulted in insightful spectra–structure–property correlations for the cocrystal and the molecular solids. Furthermore, we observed quenching of the high-temperature form of acetonitrile in the presence of the cocrystal, which supports the possibility of the existence of metastable solids as minerals on Titan. The results presented in this study further the knowledge of the putative structure and composition of the surface of Titan and, at the same time, contribute to a better understanding of the fundamental thermodynamic properties of two of the smallest organic molecules on Earth and in the Universe.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 23","pages":"9933–9939 9933–9939"},"PeriodicalIF":3.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761021","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":"Planarizing Spalled GaAs(100) Surfaces by MOVPE Growth","authors":"Gavin P. Forcade,&nbsp;William E. McMahon,&nbsp;Nicholas Yoo,&nbsp;Anica N. Neumann,&nbsp;Michelle Young,&nbsp;John Goldsmith,&nbsp;Sarah Collins,&nbsp;Karin Hinzer,&nbsp;Corinne E. Packard and Myles A. Steiner*,&nbsp;","doi":"10.1021/acs.cgd.4c0115210.1021/acs.cgd.4c01152","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01152https://doi.org/10.1021/acs.cgd.4c01152","url":null,"abstract":"<p >III–V photovoltaic devices have demonstrated exceptional performance across various applications, with controlled crystal fracturing, known as controlled spalling, emerging as a promising method to reduce costs by enabling substrate reuse. Spalling GaAs(100) substrates, a commonly used substrate in III–V photovoltaics, results in faceted ridges that must be planarized to grow high-quality photovoltaic devices. Here we demonstrate that a GaAs(100) wafer offcut toward [01̅1] and spalled toward [011] can be efficiently planarized by growing C:GaAs by metal–organic vapor phase epitaxy (MOVPE) on the surface, with up to 95% of the nominally deposited material used to fill the valleys between ridges. We find that reducing the offcut to 2° enhances the planarizing capability of C:GaAs. A surface morphology model indicates that the density of surface dangling bonds significantly influences the growth evolution of undoped GaAs surfaces. In contrast, the model suggests that the effectiveness of C:GaAs as a smoothing layer stems from modifying the atomic surface structure and, consequently, the associated sticking coefficients of the facets, which can alter the evolution of surface morphology. Our findings provide guidelines for the epitaxial planarization of semiconductor surfaces and improve the understanding of MOVPE growth on nonplanar surfaces.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 23","pages":"9975–9983 9975–9983"},"PeriodicalIF":3.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761069","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":"Bulk Crystal Growth and Single-Crystal-to-Single-Crystal Phase Transitions in the Averievite CsClCu5V2O10","authors":"Chao Liu,&nbsp;Chao Ma,&nbsp;Tieyan Chang,&nbsp;Xiaoli Wang,&nbsp;Chuanyan Fan,&nbsp;Lu Han,&nbsp;Feiyu Li,&nbsp;Shanpeng Wang,&nbsp;Yu-Sheng Chen and Junjie Zhang*,&nbsp;","doi":"10.1021/acs.cgd.4c0119510.1021/acs.cgd.4c01195","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01195https://doi.org/10.1021/acs.cgd.4c01195","url":null,"abstract":"<p >Quasi-two-dimensional averievites with triangle-Kagome-triangle trilayers are of interest due to their rich structural and magnetic transitions and strong spin frustration that are expected to host a quantum spin liquid ground state with suitable substitution or doping. Herein, we report the growth of bulk single crystals of averievite CsClCu₅V₂O₁₀ with dimensions of several millimeters on the edge in order to (1) address the open question of whether the room-temperature crystal structure is <i>P</i>3̅ m1, <i>P</i>3̅, or <i>P</i>2₁/<i>c</i> or else, (2) to elucidate the nature of phase transitions, and (3) to study direction-dependent physical properties. Single-crystal-to-single-crystal structural transitions at ∼305 and ∼127 K were observed in the averievite CsClCu₅V₂O₁₀ single crystals. The nature of the transition at ∼305 K, which was reported as a <i>P</i>3̅ m1-<i>P</i>2₁/<i>c</i> transition, was found to be a structural transition from high-temperature <i>P</i>3̅ m1 to low-temperature <i>P</i>3̅ by combining variable-temperature synchrotron X-ray single crystal and high-resolution powder diffraction. In-plane and out-of-plane magnetic susceptibility and heat capacity measurements confirm a first-order transition at 305 K, a structural transition at 127 K, and an antiferromagnetic transition at 24 K. These averievites are thus ideal model systems for a deeper understanding of structural transitions and magnetism.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9701–9708 9701–9708"},"PeriodicalIF":3.2,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671399","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":"Dirty Nucleation of Salicylic Acid","authors":"Fredrik L. Nordstrom*,&nbsp; and ,&nbsp;Yongjian Wang,&nbsp;","doi":"10.1021/acs.cgd.4c0127510.1021/acs.cgd.4c01275","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01275https://doi.org/10.1021/acs.cgd.4c01275","url":null,"abstract":"<p >Nucleation studies have been conducted on salicylic acid in the presence of solid-state miscible impurities. Crystallizations were carried out at different seed loads and supersaturation ratios while monitoring the solid and liquid phase compositions. The results show that crystallizations dominated by nucleation caused higher levels of impurity entrapment than crystallizations dominated by crystal growth at the same supersaturation ratio. The solid phase was the most enriched in impurities following nucleation and decreased linearly with the product yield until reaching thermodynamic equilibrium, as determined by the phase equilibria of the respective solid solutions. It was also found that low-level impurities were enriched to a higher degree in the early forming solid phase in crystallizations dominated by nucleation. Furthermore, metastable zone width (MZW) measurements of salicylic acid were carried out in the presence and absence of impurities. While the addition of the known solid-state miscible impurities did not exert a strong effect on the MZW, the removal of already present low-level impurities by repeated recrystallizations showed a marked increase in the apparent supersaturation ratio needed to induce primary nucleation. The results suggest that impurities accumulate in the solid phase at the onset of nucleation. The incorporation of impurities within the nuclei is expected to take place to reduce the free energy barrier to nucleation by lowering the surface free energy. At the same time, the early forming solid phase is comprised of metastable crystalline solid solution phases that are relatively disordered and exhibit higher solvent solubility than macroscale equilibrium. Comparative analyses are made to the classical and nonclassical nucleation theories conceptually, demonstrating how the level of supersaturation and material purity may impact the structural properties of the nuclei, which may lead to different nucleation pathways. Furthermore, the treatment of solid solution formation at the onset of nucleation is compared to several common empirical observations relating to the ordering and stochasticity of crystal nucleation. As an example, it is demonstrated how the creation of polymorphic metastable solid solutions following nucleation provides a thermodynamic explanation for Ostwald’s rule of stages and the appearance and disappearance of new polymorphs. Finally, the structural hysteresis obtained via the recrystallization or dissolution of crystalline solid solutions is used to explain the so-called solution memory effect.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9743–9762 9743–9762"},"PeriodicalIF":3.2,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671496","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":"Bioprocessing-Inspired Fabrication of Calcite Prismatic Layers and Growth Mechanisms","authors":"Jianhui Li,&nbsp;Qihang Wang*,&nbsp;Zhengyi Fu and Zhaoyong Zou*,&nbsp;","doi":"10.1021/acs.cgd.4c0095710.1021/acs.cgd.4c00957","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00957https://doi.org/10.1021/acs.cgd.4c00957","url":null,"abstract":"<p >Biomimetic mineralization can facilitate the fabrication of materials with intricate hierarchical structures and distinctive functional properties under ambient conditions. However, precise replication of the complex biomineralization process in vitro remains a big challenge. In this study, aimed at mimicking the biomineralization process of calcite prismatic layers of mollusk shells, a peristaltic pump was employed to slowly transport a sodium carbonate solution into a calcium-containing solution in the presence of poly(acrylic acid) (PAA). Through delicate control of the ion transport rate and reaction conditions, a calcite seed layer was first deposited on the chitosan-coated substrate, followed by the fabrication of a continuous, dense, and highly oriented shell-like calcite prismatic structure. The influences of PAA concentration and ion transportation rate on the growth kinetics and morphology of calcite were studied, showing that optimal conditions are required to form the prismatic structure. It was demonstrated that the prismatic structure started from random formation of an individual spherical disk on the seed layer, which grew larger in diameter and fused with adjacent disks. Furthermore, using confocal Raman mapping analysis, the orientation of calcite crystals at different growth stages was revealed. This study provides a novel bioprocessing-inspired strategy to fabricate a uniform calcite prismatic structure and significantly improves our understanding of the growth mechanisms.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9502–9510 9502–9510"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673971","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":"Using Chemical Substitution to Engineer Photomechanical Cinnamalmalononitrile Crystals","authors":"Thomas J. Gately,&nbsp;Cody J. Perry,&nbsp;Sophie Weiss,&nbsp;Kevin Lam,&nbsp;Imadul Islam,&nbsp;Mohammed N. Almtiri,&nbsp;Veronica Carta,&nbsp;Gregory J. O. Beran*,&nbsp;Rabih O. Al-Kaysi* and Christopher J. Bardeen*,&nbsp;","doi":"10.1021/acs.cgd.4c0103310.1021/acs.cgd.4c01033","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01033https://doi.org/10.1021/acs.cgd.4c01033","url":null,"abstract":"<p >In this work, a combined experiment and theory approach is used to study the cinnamalmalononitrile family of molecules that undergo a [2 + 2] photodimerization in the solid-state to generate photomechanical actuation. Twelve new derivatives are synthesized that exhibit two different crystal packing motifs: head-to-head (HH) in which the molecules stack with the phenyl rings on the same side of the stack, and head-to-tail (HT) in which the phenyl rings of adjacent molecules are on opposite sides. [2 + 2] photodimerization is only observed for HT packing motif. Attempts to identify chemical substitution patterns that favor the reactive HT packing based on simple steric and electrostatic considerations fail to reliably predict crystal packing, and fluorination generated both motifs in more-or-less random fashion. Empirically, substitution at the 3-position favors HT packing while substitution at the 4-position favors HH packing. Computational modeling suggests that the tendency for HH or HT packing arrangements stems from complex many-body interactions with the rest of the lattice. Modeling with periodic density functional theory shows that interactions with the rest of the lattice also explain why the HT motif is photochemically active while the HH motif is inert. Chemical substitution can also affect the theoretical photomechanical work output of the HT polymorphs. In order to obtain a reactive HT polymorph, the best strategy appears to entail placing a strong electron-withdrawing group at the 3-position, and we confirm that an HT polymorph of 3-trifluoromethyl- cinnamalmalononitrile is a highly photosalient crystal, with a predicted ideal work density of 40 MJ/m³.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9544–9555 9544–9555"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671161","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":"Competitive and Cooperative Mechanisms in the Self-Assembly Evolution of Indole Carboxylic Acid–Bipyridine Cocrystals","authors":"Di Wu,&nbsp;Hongxun Hao,&nbsp;Shuyu Li,&nbsp;Yaoguang Feng,&nbsp;Wei Chen,&nbsp;Hewei Yang,&nbsp;Ting Wang,&nbsp;Lina Zhou,&nbsp;Na Wang* and Xin Huang*,&nbsp;","doi":"10.1021/acs.cgd.4c0113210.1021/acs.cgd.4c01132","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01132https://doi.org/10.1021/acs.cgd.4c01132","url":null,"abstract":"<p >Molecular self-assembly mechanisms between cocrystal components and the evolution pathways of self-assembly are crucial for the precise design of cocrystal products. To gain a deeper insight into the molecular-level formation of cocrystals, investigations of all potential synthons were conducted using indole-2-carboxylic acid, indole-3-carboxylic acid, 2,2′-bipyridine, and 4,4′-bipyridine as model compounds. Quantum chemical calculations demonstrated the competition and cooperation mechanisms during the formation of cocrystals. While energetic and topological competition exists among synthons, the synthon capable of cooperating with other synthons, favoring the cocrystal system to achieve optimal energy state and topological structure, would be preserved within the crystals. Using Process Analysis Tools and NMR spectroscopy, the self-assembly pathway of the synthons in the solution was further elucidated. It was found to include the steps of the formation of dominant synthons caused by competition, cooperative transformation with secondary synthons, and nucleation and growth of cocrystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9601–9616 9601–9616"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671571","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":"Nineteenth Century Amorphous Calcium Carbonate.","authors":"Bart Kahr, Sophia Sburlati, Jackson Comes, John Mergo, Willem L Noorduin, Jong Seto","doi":"10.1021/acs.cgd.4c01066","DOIUrl":"10.1021/acs.cgd.4c01066","url":null,"abstract":"<p><p>The work of the English anatomist George Rainey is compared with that of the Dutch naturalist Pieter Harting. While the latter is regarded as a pioneer in biomimetic inorganic crystallography for precipitating unusual crystallographic forms that mimic the products of living organisms, the work of Rainey largely has been forgotten. In fact, Rainey first prepared amorphous calcium carbonate, a material that can be molded by organisms to form biogenic crystals. Rainey's extensive experimentation with amorphous calcareous bodies observed in a variety of organisms was at one time considered a significant and pioneering chapter in inorganic chemical morphogenesis and it should reclaim some of its former assessments. Rainey's interpretations of crystal form and the effects of gravity on crystal growth mechanisms, however, are historical curiosities that should be left behind, except to the extent that they show how the efforts of an individual may appear diminished by the dynamic process of consensus building in science. Harting also prepared amorphous calcium carbonate, but more than a decade after Rainey. While Rainey was a quiet scholar with steady habits, Harting was a statesman, a champion of the down-trodden (albeit with prejudice), a popular educator, a temperance advocate, and a sci-fi novelist, in addition to being a professor. Harting's public life may account for his outsized place in our collective memory. Rainey's synthesis of amorphous calcium carbonate in the presence of gum arabic was repeated in a modern setting. Microspheres were characterized by scanning electron microscopy, established as hollow by X-ray microtomography, and were shown to have the composition of calcium carbonate by energy dispersive X-ray analysis. They were amorphous by powder X-ray diffraction.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9301-9312"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11583214/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142708573","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":"Exploring the Spatial Arrangement of Cs-Symmetric Boron Subphthalocyanine Hybrid Crystals by Tuning Arene–Perfluoroarene Interactions","authors":"Nina F. Farac,&nbsp;Alan J. Lough and Timothy P. Bender*,&nbsp;","doi":"10.1021/acs.cgd.4c0087710.1021/acs.cgd.4c00877","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00877https://doi.org/10.1021/acs.cgd.4c00877","url":null,"abstract":"<p >Manipulating the solid-state arrangements of organic electronic materials can profoundly impact the performance of the devices in which they are utilized. This study investigates how π–π interactions, notably arene-perfluoroarene (π_H···π_F) interactions, guide the crystal structures of boron subphthalocyanine (BsubPc) hybrid derivatives by leveraging the dual dipole moments inherent in F₈BsubPcs and F₈Bsub(Pc₂–Nc₁)s. We crafted a simple molecular design varying BsubPc-type hybrids by their axial moieties and number of peripheral arene sites while maintaining a consistent count of peripheral perfluoroarene (π–hole) sites. The geometric analyses revealed that solid-state arrangements of perfluorinated BsubPc-type hybrids can be purposefully altered by introducing substituents that promote π_H···π_F stacking. We found that an additional fused benzene ring in the periphery introduced new stacking modes characterized by enhanced π–π overlap in F₈Bsub(Pc₂–Nc₁) hybrids compared to F₈BsubPcs, producing one-dimensional slip-stacked columns directed by strong-to-moderate π_H···π_F interactions. Incorporation of an axial phenol ligand in the F₈Bsub(Pc₂-Nc₁) architecture further directed new stacking patterns, transforming the framework of arene-perfluoroarene interactions from their axially halogenated counterparts. Long-range packing motifs, Hirshfeld surfaces, various solvent growth methods, serendipitous ring-opened structures, and halogen bonding were examined to understand these π_H···π_F interactions further. This work realizes the control of BsubPc hybrid spatial arrangements through strategic π–π interactions and provides avenues for potentially improved electronic functionality via highly ordered close packing configurations.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9447–9464 9447–9464"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671613","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}