Crystal Growth & Design最新文献_第7页

Crystallization of Ice Ic from Ice XVII: Outward, then Inward

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-21 DOI: 10.1021/acs.cgd.4c0173710.1021/acs.cgd.4c01737

Kenji Mochizuki*, and , Qianli Xue,

{"title":"Crystallization of Ice Ic from Ice XVII: Outward, then Inward","authors":"Kenji Mochizuki*,  and , Qianli Xue, ","doi":"10.1021/acs.cgd.4c0173710.1021/acs.cgd.4c01737","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01737https://doi.org/10.1021/acs.cgd.4c01737","url":null,"abstract":"The rare Scheiner’s halo at 28° around the sun, first reported nearly 400 years ago in Rome, suggests the presence of cubic ice (ice Ic) in the sky. However, humans only held its pure form in hand just 5 years ago, as the synthesis had been hindered by the competitive formation of hexagonal ice (ice Ih) and the mixture of hexagonal and cubic stacking sequence, resulting in stacking disordered ice (ice Isd). Since then, methods for creating pristine ice Ic from ice XVII and C2 hydrogen hydrate have been established. However, the underlying molecular mechanisms remain largely unexplored. Here, we unveil the microscopic details that enable the preferential formation of ice Ic from ice XVII through spontaneous crystallization in molecular dynamics (MD) simulations. The phase transition proceeds in two steps: first, the outward surface freezing of ice Ic within the premelting layer on the ice XVII prismatic surface, followed by the inward, layer-by-layer propagation of the stable Ic-XVII coexistence. The matching of lattice lengths and the defect-free layerwise conversion are essential. This mechanism could provide valuable insights for the precise synthetic control of target crystals over other polymorphs with similar stability, with broad applications in various fields.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1628–1635 1628–1635"},"PeriodicalIF":3.2,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547329","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

Supramolecular Organic Frameworks Based on Cyclic Aromatic Imides Tethered to Carboxylic Acid Hosts and Aromatic N-Heterocyclic Solvent Guests

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-21 DOI: 10.1021/acs.cgd.4c0162210.1021/acs.cgd.4c01622

Raju Ram Puniya, Rohit Singhal and Devendra Singh*,

{"title":"Supramolecular Organic Frameworks Based on Cyclic Aromatic Imides Tethered to Carboxylic Acid Hosts and Aromatic N-Heterocyclic Solvent Guests","authors":"Raju Ram Puniya, Rohit Singhal and Devendra Singh*, ","doi":"10.1021/acs.cgd.4c0162210.1021/acs.cgd.4c01622","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01622https://doi.org/10.1021/acs.cgd.4c01622","url":null,"abstract":"Structural aspects of eight solvates comprising two pyromellitic diimides (PMDIa and PMDIb) and two naphthalene diimides (NDIa and NDIb) tethered to isomeric carboxylic acid hosts with pyridine (py) and quinoline (qn) guests are studied. The roles of different types of noncovalent interactions such as hydrogen bonding and π-stacking in the formation of diverse supramolecular host–guest networks are described. Minor differences in the host–host and host–guest weak interactions led to the formation of both the supramolecular tight-packed networks for solvates PMDIapy, PMDIbpy, and NDIbpy and the supramolecular channeled architectures for solvates PMDIaqn, PMDIbqn, NDIapy, NDIaqn, and NDIbqn, respectively. The guest solvent molecules reside inside the channels/cavities of different dimensions in such 3D assemblies, weakly interacting with the host molecules. Remarkably, three different hydrogen bond motifs including three qn guests and a −COOH group with cyclic and discrete patterns are also identified in the quinoline solvates. DFT calculations on these unprecedented motifs authenticated the possibility of the formation of either motif in the solid state. The photoluminescence properties of the solvates revealed almost similar emissions for the solvates of PMDI hosts at 455 nm but different emissions for the solvates of NDI hosts in the range of 448–485 nm. Thermal analyses (TGA and DSC) validated the host–guest stoichiometries and decomposition temperature regions of the solvates. In general, this study looks at how weak interactions between π-electron-deficient aromatic imides and π-electron-rich aromatic guests affect the formation of supramolecular assemblies of solvates and their optical properties.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1533–1544 1533–1544"},"PeriodicalIF":3.2,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547338","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

Synthesis of High-Quality WS2 Crystals on an Ionic Liquid Surface Near Room Temperature

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-21 DOI: 10.1021/acs.cgd.4c0150910.1021/acs.cgd.4c01509

Jiawei Shen*, and , Gaoxiang Ye,

引用次数: 0

Selective Growth of Conformational Polymorphs with Distinct Morphologies by Adding Different Polymers

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 DOI: 10.1021/acs.cgd.4c0163410.1021/acs.cgd.4c01634

Zaiqing Yang, Zhiao Zhuo, Jiawei Lin, Songgu Wu* and Junbo Gong,

{"title":"Selective Growth of Conformational Polymorphs with Distinct Morphologies by Adding Different Polymers","authors":"Zaiqing Yang, Zhiao Zhuo, Jiawei Lin, Songgu Wu* and Junbo Gong, ","doi":"10.1021/acs.cgd.4c0163410.1021/acs.cgd.4c01634","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01634https://doi.org/10.1021/acs.cgd.4c01634","url":null,"abstract":"Understanding the relationship between polymorphs and crystal growth is crucial for polymorph control. Here, the polymorph growth of pimelic acid (DA7) was investigated in aqueous solutions containing different polymers. The stable form III was obtained in an aqueous solution at a supersaturation level of S = 1.3 at 298.15 K. However, DA7-crystallized into form II in the presence of polyacrylamide (PAM) or poly(vinyl alcohol) (PVA). Moreover, form II developed distinct morphologies in PAM and PVA aqueous solutions. Face indexing according to single-crystal X-ray diffraction (SCXRD) revealed that two form II crystals had completely different faces. In situ crystal growth monitoring confirmed that the specific growth of faces was the key factor in determining the resulting polymorph. The preferential adsorption of additives on certain faces governed their growth according to molecular dynamics simulation. Additionally, the additives can modify the surface roughness of the crystals, thereby affecting their growth. Our work demonstrated that the crystallization of the targeted polymorph product can be achieved via varied growth pathways.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1556–1564 1556–1564"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547497","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

Intercalation of Neutral Guests in Pillared Salt Cocrystals of 5-Ureidosalyclic Acid.

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 eCollection Date: 2025-03-05 DOI: 10.1021/acs.cgd.4c01715

Stuart R Kennedy, Toby J Blundell, Elizabeth F Henderson, Adeline P Miquelot, Jonathan W Steed

{"title":"Intercalation of Neutral Guests in Pillared Salt Cocrystals of 5-Ureidosalyclic Acid.","authors":"Stuart R Kennedy, Toby J Blundell, Elizabeth F Henderson, Adeline P Miquelot, Jonathan W Steed","doi":"10.1021/acs.cgd.4c01715","DOIUrl":"10.1021/acs.cgd.4c01715","url":null,"abstract":"The salts of 5-ureidosalyclic acid (5-USA) form a range of pillared salt inclusion complexes from basic solvents, namely, triethylamine, piperidine, morpholine, and 4-ethylpyridine. The triethylamine derivative is unsolvated, while the other salts include 1-3 solvent molecules of formula XH+(5-USA-H)-·nX (X = morpholine, n = 1, 2, and 3 (2a - 2c); X = 4-ethylpyridine, n = 1 (3) and X = piperidine, n = 2.5 (4)). The morpholine salt expands the layered structure to include 1, 2, or 3 guests. The 5-USA anion can also act as a bidentate ligand for manganese(III), again forming highly solvated inclusion complex anions [Mn(5-USA-H)2(Solv)2]-. When interacting strongly with the countercation, the 5-USA anions adopt an unusual cis carboxylate isomer form, whereas the morpholinium salt solvate (H-morpholine)[Mn(5-USA-H)2(morpholine)2]·2(morpholine) (5c) is trans. The soft, plastic crystals of this complex gradually desolvate, losing channel morpholine and ultimately spontaneously recrystallizing as the 5-USA salt dimorpholine inclusion complex 2b. The complex hydrogen-bonded, pillared 5-USA salts illustrate a design concept for intercalated materials of forming charged, planar layers that leave the charge-balancing counterion exposed, such that interlayer guest species must be incorporated to effectively solvate the charged moieties.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1614-1621"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11887045/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583939","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}

引用次数: 0

Controlling Energetic Crystal Morphology Using Tailored Polymeric Additives

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 DOI: 10.1021/acs.cgd.5c0004910.1021/acs.cgd.5c00049

Shelby T. Nicolau, and , Adam J. Matzger*,

{"title":"Controlling Energetic Crystal Morphology Using Tailored Polymeric Additives","authors":"Shelby T. Nicolau,  and , Adam J. Matzger*, ","doi":"10.1021/acs.cgd.5c0004910.1021/acs.cgd.5c00049","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00049https://doi.org/10.1021/acs.cgd.5c00049","url":null,"abstract":"While much emphasis is placed on chemical structure when deploying a compound for a given application, the shape in which the compound crystallizes, its morphology, has also proven influential in the control of properties that span fields from pharmaceuticals to energetic materials. Outside of processability, crystal morphology is vital for energetic materials because of its ties to explosive sensitivity and performance, stemming from the influence of morphology on the crystal packing density. Morphology control is commonly accomplished by altering crystallization conditions (e.g., solvent, temperature, and supersaturation) in order to alter the relative growth rates of crystal faces. Less commonly employed to control the morphology is the use of additives. Herein, a methodology for selecting additives to control the morphology of explosives is investigated based on targeting interactions present in cocrystals. Specifically, 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) was used as a model compound; three polymers were selected and successfully implemented as soluble, face-selective shape modifiers for HMX, a structurally similar analogue 3,3,7,7-tetrakis(difluoramino)octahydro-1,5-dinitro-1,5-diazocine (HNFX), and nitroguanidine (NQ). These results demonstrate morphology modification in both desirable (needle-to-block) and undesirable (block-to-needle) directions and illustrate a general design approach for crystal shape engineering applicable to energetic materials.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1667–1674 1667–1674"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547172","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

Intercalation of Neutral Guests in Pillared Salt Cocrystals of 5-Ureidosalyclic Acid

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 DOI: 10.1021/acs.cgd.4c0171510.1021/acs.cgd.4c01715

Stuart R. Kennedy, Toby J. Blundell, Elizabeth F. Henderson, Adeline P. Miquelot and Jonathan W. Steed*,

{"title":"Intercalation of Neutral Guests in Pillared Salt Cocrystals of 5-Ureidosalyclic Acid","authors":"Stuart R. Kennedy, Toby J. Blundell, Elizabeth F. Henderson, Adeline P. Miquelot and Jonathan W. Steed*, ","doi":"10.1021/acs.cgd.4c0171510.1021/acs.cgd.4c01715","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01715https://doi.org/10.1021/acs.cgd.4c01715","url":null,"abstract":"The salts of 5-ureidosalyclic acid (5-USA) form a range of pillared salt inclusion complexes from basic solvents, namely, triethylamine, piperidine, morpholine, and 4-ethylpyridine. The triethylamine derivative is unsolvated, while the other salts include 1–3 solvent molecules of formula XH+(5-USA-H)−·nX (X = morpholine, n = 1, 2, and 3 (2a – 2c); X = 4-ethylpyridine, n = 1 (3) and X = piperidine, n = 2.5 (4)). The morpholine salt expands the layered structure to include 1, 2, or 3 guests. The 5-USA anion can also act as a bidentate ligand for manganese(III), again forming highly solvated inclusion complex anions [Mn(5-USA-H)2(Solv)2]−. When interacting strongly with the countercation, the 5-USA anions adopt an unusual cis carboxylate isomer form, whereas the morpholinium salt solvate (H-morpholine)[Mn(5-USA-H)2(morpholine)2]·2(morpholine) (5c) is trans. The soft, plastic crystals of this complex gradually desolvate, losing channel morpholine and ultimately spontaneously recrystallizing as the 5-USA salt dimorpholine inclusion complex 2b. The complex hydrogen-bonded, pillared 5-USA salts illustrate a design concept for intercalated materials of forming charged, planar layers that leave the charge-balancing counterion exposed, such that interlayer guest species must be incorporated to effectively solvate the charged moieties.Crystals of a urea−salicylic acid derivative form charged, planar layers that leave the counterion exposed causing incorporation of further interlayer guests. One such layered cocrystal crystallizes from desolvation and deliquescence of plastic crystals of a manganese complex of the urea−salicylic acid ligand.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1614–1621 1614–1621"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01715","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547250","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}

引用次数: 0

Calcium Medronate-Based Metal–Organic Frameworks as Multifunctional Biomaterials

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 DOI: 10.1021/acs.cgd.4c0147810.1021/acs.cgd.4c01478

Pablo Salcedo-Abraira, María Fernández-Grajera, Francisco A. Guerrero-Román, Antonio Rodríguez-Diéguez, Veronica Luque-Agudo, María Luisa González-Martín, Amparo M. Gallardo-Moreno* and Sara Rojas*,

{"title":"Calcium Medronate-Based Metal–Organic Frameworks as Multifunctional Biomaterials","authors":"Pablo Salcedo-Abraira, María Fernández-Grajera, Francisco A. Guerrero-Román, Antonio Rodríguez-Diéguez, Veronica Luque-Agudo, María Luisa González-Martín, Amparo M. Gallardo-Moreno* and Sara Rojas*, ","doi":"10.1021/acs.cgd.4c0147810.1021/acs.cgd.4c01478","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01478https://doi.org/10.1021/acs.cgd.4c01478","url":null,"abstract":"Metal–organic frameworks (MOFs) can be prepared from bioactive molecules, which are released during the degradation of the material in the body. Particularly, MOFs have recently emerged as bisphosphonate (BP) drug delivery systems. In this work, two novel MOFs based on the smallest bisphosphonate medronic acid (MA) and calcium with formulas [Ca(CH4O6P2)·H2O] (GR-MOF-23) and [Ca(CH4O6P2)·CH3OH] (GR-MOF-24) in aqueous and/or methanolic solutions at room temperature were synthesized and fully characterized. The stability test performed in simulated physiological conditions (a phosphate buffer saline (PBS, pH = 7.4, 10 mM) solution at 37 °C) showed a progressive Ca2+ leaching from both GR-MOF-23 and GR-MOF-24, achieving 38.0 ± 2.8 and 35.8 ± 3.9% release of calcium after 1 week of suspension. Interestingly, the recovered solid residues from the stability tests were identified as apatite and calcium phosphate phases, which might facilitate the formation of bone apatite and collagen. The antibacterial activity of GR-MOF-23 and GR-MOF-24 was investigated against Escherichia coli and Staphylococcus aureus, among the most relevant human pathogens, causing a wide variety of infections in bone fracture in osteoporosis and prosthesis. While both materials exhibited bacteria growth inhibition, GR-MOF-24 also showed a bactericide action, likely due to a more progressive release of Ca2+, which is the ion related to the improved stability of the biofilm. These innovative materials present exciting opportunities for developing antibacterial surfaces in prosthetics and the treatment of bone fracture infections.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1415–1422 1415–1422"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547642","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

First-Principles Approach to Assess the Viability of MoOPO4 as an Electrode Material for Mg-Ion Batteries

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-20 DOI: 10.1021/acs.cgd.4c0163110.1021/acs.cgd.4c01631

Jingdong Yang*, Jiaxin Wen, Junliu Ye, Xiaoyang Dong, Guangshen Huang, Jingfeng Wang, Jinxing Wang* and Fusheng Pan,

{"title":"First-Principles Approach to Assess the Viability of MoOPO4 as an Electrode Material for Mg-Ion Batteries","authors":"Jingdong Yang*, Jiaxin Wen, Junliu Ye, Xiaoyang Dong, Guangshen Huang, Jingfeng Wang, Jinxing Wang* and Fusheng Pan, ","doi":"10.1021/acs.cgd.4c0163110.1021/acs.cgd.4c01631","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01631https://doi.org/10.1021/acs.cgd.4c01631","url":null,"abstract":"Searching for novel high-performance magnesium battery cathodes is an attractive subject in the development of energy storage devices. In this work, density functional theory calculations are employed to predict the theoretical feasibility of bulk MoOPO4 (B-MoOPO4) and monolayer MoOPO4 (M-MoOPO4) as magnesium battery electrodes. The structural and electronic properties of both MoOPO4 are investigated, with a particular emphasis on the magnesium storage and diffusion behaviors within the structures. The results reveal that both B-MoOPO4 and M-MoOPO4 exhibit favorable electronic conductivity and low magnesium ion diffusion barriers, suggesting their potential for high rate performance. Furthermore, both B-MoOPO4 and M-MoVOPO4 possess a substantial number of active sites available for magnesium storage, with theoretical capacities of 259 mAh/g and 130 mAh/g, respectively, and theoretical energy densities reaching 417 and 73 Wh/kg, respectively. Open-circuit voltage calculations indicate a magnesiation voltage window of 1.95 to 1.01 V for B-MoOPO4 and a voltage window of 0.67 to 0.44 V for M-MoOPO4. In conclusion, both B-MoOPO4 and M-MoOPO4 demonstrate the feasibility of serving as magnesium battery electrodes. B-MoOPO4 is better suited as a cathode due to its higher intercalation potential, while M-MoOPO4, with its lower magnesium intercalation potential, is more inclined to serve as an anode.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1545–1555 1545–1555"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547647","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

Mechanochemically Driven C–C Bond Formation via Cu-Complex-Functionalized Polyoxoniobate under Solvent-Free Conditions

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-19 DOI: 10.1021/acs.cgd.5c0002110.1021/acs.cgd.5c00021

Weina Cai, Hongrui Tian*, Zouguang Han, Zuming Rao, Baokuan Chen* and Yanfeng Bi*,

{"title":"Mechanochemically Driven C–C Bond Formation via Cu-Complex-Functionalized Polyoxoniobate under Solvent-Free Conditions","authors":"Weina Cai, Hongrui Tian*, Zouguang Han, Zuming Rao, Baokuan Chen* and Yanfeng Bi*, ","doi":"10.1021/acs.cgd.5c0002110.1021/acs.cgd.5c00021","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00021https://doi.org/10.1021/acs.cgd.5c00021","url":null,"abstract":"Developing a mechanochemical, solvent-free approach for forming C–C bonds in place of traditional solvent-based synthesis is significant for green chemistry. Herein, a novel Cu-complex-functionalized polyoxoniobate-based hybrid material [Cu(tpy)2]{[Cu(tpy)(H2O)]2[Nb10O28]}·5.5H2O (1, tpy = 2,2′:6′,2″-terpyridine) is successfully synthesized and thoroughly characterized. 1 displays excellent thermal and solvent stability and is highly mechanical force tolerant. Catalytic studies reveal that 1 can catalyze the Knoevenagel condensations of a series of aromatic aldehydes with malononitrile to build C–C bond compounds under mechanochemical ball milling conditions. The catalytic system is conducted with no additional heating, with a lower oscillating frequency, and without a solvent. The remarkable performance of catalyst 1 can be attributed to two factors: one is the sufficient contact between the catalyst and reagents facilitated by mechanical force, as well as the preactivated catalyst by it; the other is the synergistic effect of the Lewis acid–base sites (Cu2+ and [Nb10O28]6–) within the catalyst. The catalyst exhibits outstanding recyclability and can be applied to gram-scale reactions. To the best of our knowledge, this work represents the first example of a mechanochemically driven solvent-free organic transformation using a polyoxometalate-based catalyst.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1636–1643 1636–1643"},"PeriodicalIF":3.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547238","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