Crystal Growth & Design最新文献_第3页

Regulation of Dimensionality and Energetic Performance in Silver(I) Coordination Polymers via Steric Effects of Heteroatoms 杂原子空间效应对银(I)配位聚合物维数和能量性能的调控

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-02 DOI: 10.1021/acs.cgd.6c00776

Chao Zhang, Tingwei Wang, Shaoqun Li, Cong Li, Zujia Lu, Meiqi Xu, Binshan Zhao, Qiyao Yu, Jianguo Zhang

{"title":"Regulation of Dimensionality and Energetic Performance in Silver(I) Coordination Polymers via Steric Effects of Heteroatoms","authors":"Chao Zhang, Tingwei Wang, Shaoqun Li, Cong Li, Zujia Lu, Meiqi Xu, Binshan Zhao, Qiyao Yu, Jianguo Zhang","doi":"10.1021/acs.cgd.6c00776","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00776","url":null,"abstract":"Energetic coordination compounds (ECCs) offer a new paradigm for designing high-energy and high-safety energetic materials by integrating the catalytic activity of metal centers with the structural tunability of ligands. Inspired by the regulation of coordination modes through electronic effects, oxazole-2-carbohydrazide (OZ-2-CA) and thiazole-2-carbohydrazide (SZ-2-CA) were selected as ligands in this study to synthesize two novel ECCs, [Ag(OZ-2-CA)ClO4]n (ECC-1) and Ag2(SZ-2-CA)2(ClO4)2 (ECC-2) through self-assembly. Single-crystal X-ray diffraction revealed that the planarity of the ligand framework dictates the differentiation in coordination dimensionality. The rigid OZ-2-CA enables the formation of a one-dimensional helical chain structure in ECC-1, whereas the twisted SZ-2-CA constrains ECC-2 to a zero-dimensional discrete dimer. By combining theoretical calculations and experimental characterization, the structure−property relationship between ligand geometry, caused by heteroatom size, and crystal packing as well as macroscopic performance was elucidated. Benefiting from a higher density (2.475 g cm−3) and favorable oxygen balance (−21.53%), ECC-1 exhibits outstanding detonation performance (D = 6.24 km s−1, P = 22.26 GPa) and moderate mechanical sensitivity (IS = 4.2 J). In contrast, ECC-2 shows considerably reduced performance due to a more negative enthalpy of formation (−504.0 kJ·mol−1) and poorer oxygen balance, attributed to the introduction of sulfur atoms.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8195–8203"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221986","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}

引用次数: 0

Regulation Mechanism of Cusp-Magnetic-Field-Induced Thermoelectric Magnetic Convection on Dendrite Refinement and Uniformity in Single-Crystal Superalloys 尖磁场诱导热电磁力对流对单晶高温合金枝晶细化和均匀性的调节机制

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-10 DOI: 10.1021/acs.cgd.6c01114

Hongbin Yu, Yufeng Yang, Hongda Kang, Chuanxin Shi, Weili Ren, Congjiang Zhang, Tianhan He, Biao Ding, Zhe Shen, Tianxiang Zheng, Ang Zhang, Yunbo Zhong

{"title":"Regulation Mechanism of Cusp-Magnetic-Field-Induced Thermoelectric Magnetic Convection on Dendrite Refinement and Uniformity in Single-Crystal Superalloys","authors":"Hongbin Yu, Yufeng Yang, Hongda Kang, Chuanxin Shi, Weili Ren, Congjiang Zhang, Tianhan He, Biao Ding, Zhe Shen, Tianxiang Zheng, Ang Zhang, Yunbo Zhong","doi":"10.1021/acs.cgd.6c01114","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01114","url":null,"abstract":"The refinement and uniformity of dendrite microstructures in single-crystal (SC) superalloys directly determine their high-temperature mechanical properties and service reliability. In conventional directional solidification (DS) processes, the macroscopic temperature and solute fields ahead of the solid−liquid (SL) interface are inherently spatially non-uniform, resulting in pronounced variations in primary dendrite arm spacing (PDAS) at different locations. This poses a significant challenge to achieving effective control over the overall uniformity of the solidification microstructure. In this study, leveraging the unique configuration of the Cusp magnetic field (CMF), we investigated its influence on dendritic growth behavior in directionally solidified SC superalloy specimens with different diameters. The results demonstrate that the CMF reduces the PDAS and improves its spatial distribution uniformity. Moreover, both effects are enhanced with increasing specimen diameter. Quenching experiments combined with macroscale multiphysics simulations reveal that thermoelectric magnetic convection induced by the CMF effectively compensates for the non-uniform thermal field from radiative heat transfer, thereby driving the macroscopic interface toward a planar morphology. Phase-field simulations further indicate that, the differences in dendrite tip migration kinetics at different positions are reduced under the relatively planar interface, thereby synergistically promoting dendrite refinement and homogenization. This work provides a new theoretical basis for the dendrite refinement and homogenization in SC superalloys through macroscopic SL interface engineering.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8552–8566"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221979","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}

引用次数: 0

Analyzing the Impact of Sorbent Fluorophilicity on the Adsorption of Tetrafluoromethane in a Metal−Organic Framework 吸附剂亲氟性对金属-有机骨架吸附四氟甲烷的影响分析

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-02 DOI: 10.1021/acs.cgd.6c01097

Bevan S. Whitehead, Bittu Chandra, William W. Brennessel, Brandon R. Barnett

{"title":"Analyzing the Impact of Sorbent Fluorophilicity on the Adsorption of Tetrafluoromethane in a Metal−Organic Framework","authors":"Bevan S. Whitehead, Bittu Chandra, William W. Brennessel, Brandon R. Barnett","doi":"10.1021/acs.cgd.6c01097","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01097","url":null,"abstract":"Perfluorinated and highly fluorinated organic molecules exhibit fluorophilic behavior, or a preference for partitioning with fluorinated phases over lipophilic or hydrophilic phases. Fluorophilic interactions leverage local charge separations that arise from polarized C−F bonds. For larger perfluorinated molecules, the cumulative strength of these interactions can drive selective partitioning with fluorophilic surfaces, such as those within a porous sorbent. However, it is presently unclear whether tetrafluoromethane (CF4), the smallest perfluorocarbon and a potent greenhouse gas, can engage appreciably in fluorophilic interactions with a highly fluorinated surface. Herein, we report a library of metal−organic frameworks (MOFs) that modulate the length of either fluorophilic or lipophilic alkyl chains tethered within mesoporous channels. Our approach relies on postsynthetic amine coordination, leaving the base framework constant across the series and allowing for comparisons that obviate large changes in pore shape or structure. We find that fluorophilic sorbent character is correlated to, at most, a modest increase in affinity for CF4. Very similar results are also observed for the non-fluorinated adsorbate methane (CH4). These findings have implications for the design of adsorptive separation schemes involving both fluorinated and non-fluorinated non-polar gases.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8511–8521"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221983","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}

引用次数: 0

MOF-On-MOF Heterostructure Coupled with Polyaniline as Advanced Electrode for High-Energy-Density Supercapacitors MOF-On-MOF异质结构耦合聚苯胺作为高能量密度超级电容器的先进电极

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-03 DOI: 10.1021/acs.cgd.6c00855

Ping-Ping Sun, Yun-Heng Li, Jin-Juan Xing, Hai-Yan Liu

{"title":"MOF-On-MOF Heterostructure Coupled with Polyaniline as Advanced Electrode for High-Energy-Density Supercapacitors","authors":"Ping-Ping Sun, Yun-Heng Li, Jin-Juan Xing, Hai-Yan Liu","doi":"10.1021/acs.cgd.6c00855","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00855","url":null,"abstract":"This study designs a MOF-on-MOF heterostructure coupled with polyaniline as a high-performance electrode for high-energy-density supercapacitors. Flower-like BTC-Ni was synthesized by a hydrothermal method, followed by in situ growth of ZIF-67 to construct a hierarchical heterojunction, and then coated with polyaniline via electropolymerization to obtain the ternary composite BTC-Ni/ZIF-67@PANI. Systematic characterizations including X-ray absorption fine structure (EXAFS) and wavelet transform reveal that Ni exists in the form of Ni−O coordination and Co exists in the form of Co−N coordination, both highly dispersed without metal agglomeration, providing abundant bimetallic active sites. The heterointerface optimizes the electronic structure, strengthens OH− adsorption, and accelerates charge transfer. The PANI layer forms a continuous conductive network, improves conductivity, supplies extra pseudocapacitance, and alleviates volume expansion during cycling. Electrochemical tests show that the composite exhibits high specific capacitance, excellent rate performance, and 85.9% capacitance retention after 10,000 cycles at 5 A/g. The assembled asymmetric supercapacitor achieves a voltage window of 1.6 V and an energy density of 67.28 Wh/kg at 800 W/kg. This work provides a feasible strategy for constructing advanced MOF-based electrodes with clear coordination environment and excellent energy storage performance.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8252–8264"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222012","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}

引用次数: 0

Composition-Tuned Dual-Mode Photodetection in BiS1−xSexI Crystals: From Bias-Driven Photoconductivity to Self-Powered Photothermoelectrics BiS1−xSexI晶体的成分调谐双模光探测：从偏置驱动的光导到自供电的光热电

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-05 DOI: 10.1021/acs.cgd.6c00980

Bao Xiao, Hong-Tao Jiang, Wenzhuo Han, Di Sun, Ning Li, Yiru Tai, Yang-Yang Lv, Bin-Bin Zhang

{"title":"Composition-Tuned Dual-Mode Photodetection in BiS1−xSexI Crystals: From Bias-Driven Photoconductivity to Self-Powered Photothermoelectrics","authors":"Bao Xiao, Hong-Tao Jiang, Wenzhuo Han, Di Sun, Ning Li, Yiru Tai, Yang-Yang Lv, Bin-Bin Zhang","doi":"10.1021/acs.cgd.6c00980","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00980","url":null,"abstract":"Bismuth-based chalcohalides have garnered significant attention for optoelectronic applications due to their low toxicity and excellent photophysical properties. Herein, high-quality BiS1−xSexI (0 ≤ x ≤ 1) single crystals were successfully grown via physical vapor transport (PVT) method. Se element substitution not only tunes the bandgap from 1.53 eV to 1.29 eV but also reduces the resistivity by over 6 orders of magnitude, enabling distinct photodetection mechanisms. For the end-member BiSI (BiS1−xSexI, x = 0), the device operates in a bias-dependent photoconductive mode, achieving a high responsivity of 1 mA/W at 10 V bias under 425 nm illumination. Conversely, for Se-rich compositions like BiS1−xSexI (x = 0.75, and 1), the photothermoelectric (PTE) effect dominates, allowing for sensitive self-powered broadband detection. The optimized PTE device exhibits stable ON-OFF switching under 425 nm illumination, yielding a responsivity of 227 mV/W with a specific detectivity of 6.5 × 106 Jones. These results highlight the versatility of BiS1−xSexI crystals, offering a pathway to switch between high-gain photoconductors and broadband, self-powered PTE detectors through compositional engineering.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8393–8402"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222013","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}

引用次数: 0

Atmosphere-Induced Preferentially Oriented Growth: Crystalline Evolution and a Tunable Optical Band Gap in Bismuth-Derived β-Bi2O3 Films 大气诱导的优先取向生长：铋衍生β-Bi2O3薄膜的晶体演化和可调光学带隙

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-12 DOI: 10.1021/acs.cgd.6c00563

Muyan Dai, Tong Zhang, Ruobing Feng, Ning Zhang, Nan Wang

{"title":"Atmosphere-Induced Preferentially Oriented Growth: Crystalline Evolution and a Tunable Optical Band Gap in Bismuth-Derived β-Bi2O3 Films","authors":"Muyan Dai, Tong Zhang, Ruobing Feng, Ning Zhang, Nan Wang","doi":"10.1021/acs.cgd.6c00563","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00563","url":null,"abstract":"The controllable synthesis of β-Bi2O3 thin films with specific crystallographic orientations is essential for optoelectronic device applications. However, achieving precise orientation control by modulating the growth conditions remains a significant challenge. In this work, we demonstrate that the oxidizing atmosphere is a critical determinant in the oxidation of bismuth (Bi) metal, dictating a transition from thermodynamics-driven epitaxial growth to kinetics-dominated non-epitaxial growth of β-Bi2O3 films. In an oxygen-deficient atmosphere, the reaction is thermodynamically controlled. In this regime, β-Bi2O3 grows via a mechanism on the Bi(003) surface, guided by lattice matching, to form a dense film with a dominant (201) orientation. This process follows a specific crystallographic relationship: Bi(003)//β-Bi2O3(002). In contrast, under oxygen-rich and air atmospheres, the reaction becomes kinetically controlled, where the competition among growth rates of different crystal facets prevails. This leads to a shift in the preferred orientation toward a mixed feature of the (002) and (220) planes. Such atmosphere-induced microstructural evolution directly modulates the optical properties of the films. The preferred oriented-growth (201) film exhibits an optical band gap of approximately 2.64 eV, which is slightly wider than the intrinsic value. Conversely, films grown under oxygen-rich and air atmospheres show a broader band gap of approximately 2.83 eV. This work elucidates the physical origin of orientation competition during Bi oxidation and establishes a universal strategy for tailoring the crystal orientation, microstructure, and optical band gap of metal-oxide films simply by engineering the oxidizing atmosphere.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8116–8128"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222075","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}

引用次数: 0

III-V Selective Area Growth by Molecular Beam Epitaxy for Integrated Quantum Systems and Applications 集成量子系统中分子束外延的选择性面积生长及其应用

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-08 DOI: 10.1021/acs.cgd.6c00924

Ashlee M. García, Alec M. Skipper, Daniel J. Ironside, Devon O. Lee, Minjoo L. Lee, Seth R. Bank, R. Corey White

{"title":"III-V Selective Area Growth by Molecular Beam Epitaxy for Integrated Quantum Systems and Applications","authors":"Ashlee M. García, Alec M. Skipper, Daniel J. Ironside, Devon O. Lee, Minjoo L. Lee, Seth R. Bank, R. Corey White","doi":"10.1021/acs.cgd.6c00924","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00924","url":null,"abstract":"To realize practical quantum information processing systems with high fidelity, disparate materials and components must be integrated on a scalable, unified platform. Among these, III-V alloys with their widely tunable optical properties and advantageous transport properties are strong candidates for the generation, manipulation, and detection of qubit states. Here, we present selective area growth (SAG) of III-V semiconductors by molecular beam epitaxy (MBE) as a uniquely well-advantaged approach to overcome the limitations of heterogeneous and hybrid integration. We review the underlying mechanisms of SAG by MBE and notable recent advancements enabled by this technique. Then, we discuss III-V components that are of utmost importance for various quantum architectures including nanowires for hosting Majorana modes, quantum dots for both classical lasers and single-photon generation, nonlinear nanophotonics for the manipulation of light, and avalanche photodiodes for single photon counting. For each device architecture, we review recent advances in the performance of these components for quantum applications and identify key opportunities for SAG to be applied to realize scalable integrated systems.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"7991–8014"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221945","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}

引用次数: 0

Halogen Substitution-Controlled Phase Transition, Dielectric Anomaly, and SHG Switching in Ga-Based Hybrid Molecular Ferroelectrics 基于ga的杂化铁电分子中卤素取代控制的相变、介电异常和SHG开关

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-05 DOI: 10.1021/acs.cgd.6c00854

Mingjun Zou, Yuhang Wu, Zhishuo Zhang, Guoyong Chen, An Duan, Zhirong Zhong, Lin Zhou, Wenjing Guo, Zhenhong Wei, Hu Cai

{"title":"Halogen Substitution-Controlled Phase Transition, Dielectric Anomaly, and SHG Switching in Ga-Based Hybrid Molecular Ferroelectrics","authors":"Mingjun Zou, Yuhang Wu, Zhishuo Zhang, Guoyong Chen, An Duan, Zhirong Zhong, Lin Zhou, Wenjing Guo, Zhenhong Wei, Hu Cai","doi":"10.1021/acs.cgd.6c00854","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00854","url":null,"abstract":"Halogen engineering provides a versatile strategy for modulating intermolecular interactions and structural flexibility, enabling precise control over phase transition behaviors and functional responses. In this work, using 1,5-diazabicyclo[3.3.0]nonane (1,5−3.3.0-dabcn) as the organic scaffold, three organic−inorganic hybrid switchable phase-change materials, [1,5−3.3.0-dabcn-CH2Br][GaCl4] (1), [1,5−3.3.0-dabcn-CH2Br][GaBr4] (2), and [1,5−3.3.0-dabcn-CH2Br][GaI4] (3), were successfully synthesized via reaction with GaX3 (X = Cl, Br, I) in aqueous HX solutions. Compounds 1 and 2 exhibit reversible phase transitions, distinct dielectric anomalies, temperature-triggered second-harmonic generation (SHG) switching, and room-temperature ferroelectricity. In contrast, compound 3 shows only phase transition behavior without ferroelectricity or SHG activity. Comparative structural and Hirshfeld surface analyses reveal that halogen substitution systematically alters the strength and distribution of H···X hydrogen bonds, as well as the packing symmetry, thereby governing the observed functional evolution from polar (1, 2) to centrosymmetric (3) structures. This study demonstrates an effective molecular design strategy for constructing gallium halide hybrid materials with tunable physical properties.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8243–8251"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221902","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}

引用次数: 0

Effect of Substituent Position on the Polymorphism of Salicylaniline Derivatives 取代基位置对水杨胺衍生物多态性的影响

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-09 DOI: 10.1021/acs.cgd.6c00829

Xin Li, Zi Wang, Ying Hu, Ting Wang, Ying Song, Yang Yang, Deyin Wang, Zaixiang Zhang

{"title":"Effect of Substituent Position on the Polymorphism of Salicylaniline Derivatives","authors":"Xin Li, Zi Wang, Ying Hu, Ting Wang, Ying Song, Yang Yang, Deyin Wang, Zaixiang Zhang","doi":"10.1021/acs.cgd.6c00829","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00829","url":null,"abstract":"To elucidate how substituent position regulates polymorphic crystallization, two chlorinated salicylideneaniline positional isomers4CC (4-chloro) and 5CC (5-chloro)were investigated. How the substituent position modulates the pathway from electronic structure to crystallization kinetics has not been systematically addressed. Electrostatic potential analysis and a Cambridge Structural Database survey reveal conformational dimorphisma twisted yellow form and a nearly planar orange formas a general feature of this compound class, with the substituent position fine-tuning the molecular electronic structure without fundamentally altering it. Both isomers share a twisted global-minimum conformation (≈40°) with low interconversion barriers. Although the yellow polymorph is metastable for both isomers, the lattice energy difference between the orange and yellow forms is substantially greater for 5CC (ΔUlat ≈ 4.8 kJ·mol−1) than for 4CC (≈0.1 kJ·mol−1), and the 5-chloro isomer exhibits systematically lower solubility, indicating selective stabilization of the thermodynamically favored polymorph. Lattice energy decomposition identifies dispersion forces as the dominant cohesive contribution, with electrostatic interactions playing a secondary but discriminating role. Kinetically, the 4-chloro isomer exhibits a lower crystal−liquid interfacial tension than the 5-chloro counterpart for the yellow polymorphs (1.05 vs. 1.43 mJ·m−2), correlating with shorter nucleation induction times, yet slower crystal growth ratesrevealing a complementarity between nucleation and growth. These findings establish substituent position as a versatile structural variable that, through modulation of conformation, intermolecular interactions, and interfacial energetics, differentially governs the thermodynamic stability and crystallization kinetics of 4CC and 5CC.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8204–8218"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222037","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}

引用次数: 0

A Journey through Solvent Space: New Solvates of Probucol 溶剂空间之旅：普罗布考的新溶剂

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-05 DOI: 10.1021/acs.cgd.6c01115

João A. Baptista, Mário T. S. Rosado, Ricardo A. E. Castro, Elvira Fantechi, Laura Chelazzi, Samuele Ciattini, M. Ermelinda S. Eusébio

{"title":"A Journey through Solvent Space: New Solvates of Probucol","authors":"João A. Baptista, Mário T. S. Rosado, Ricardo A. E. Castro, Elvira Fantechi, Laura Chelazzi, Samuele Ciattini, M. Ermelinda S. Eusébio","doi":"10.1021/acs.cgd.6c01115","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01115","url":null,"abstract":"A systematic expansion of the solid-form landscape of the antihyperlipidemic drug probucol was carried out using a diverse set of solvents spanning a broad physicochemical space, providing insight into the formation of probucol solvated forms. Five new solvates were discovered (with cyclohexane, carbon tetrachloride, tetrahydrofuran, 1,4-dioxan and dimethylsulfoxide), and comprehensively characterized, including their crystal structures, infrared spectra, thermal behaviour and solid-state stability. The results show that solvate formation is governed primarily by solvent molecular size and shape, together with hydrogen-bond acceptor ability. Solvates were obtained with small apolar solvents, and with small hydrogen-bond accepting molecules capable of accessing the sterically hindered hydroxyl groups of probucol and forming stabilizing hydrogen-bonding intermolecular interactions. In contrast, solvate formation was not observed for hydrogen-bond donor solvents or for larger, more flexible solvent molecules. The stability of the solvated forms was assessed under controlled temperature and relative humidity conditions, revealing a common dessolvation pathway (except for the dimethylsulfoxide solvate, which remained stable after 15 days), albeit at different rates, leading to the formation probucol polymorph II. Competitive slurry experiments carried out in selected binary solvent mixtures confirmed that the domains of stability of the solvates are determined by their solubilities in the respective pure solvent.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8522–8535"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222019","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}

引用次数: 0