首页 > 最新文献

CrystEngComm最新文献

英文 中文
Structure and electrical properties of Cu, Bi and Mn co-doped K0.5Na0.5NbO3 single crystals grown by seed-free solid state crystal growth method 无种子固态晶体生长法生长的铜、铋和锰共掺杂 K0.5Na0.5NbO3 单晶的结构和电学特性
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1039/d4ce00502c
Yuan Xu, Minhong Jiang, Xinkang Liu, Yujiao Zeng, Shixuan Cao, Yujiao Ouyang, Jianwei Song, Guang-Hui Rao
K0.5Na0.5NbO3 (KNN) crystals have great application prospects due to their excellent piezoelectric properties, high Curie temperature, and environmental friendliness. Currently, KNN crystals grown by the seed-free solid-state crystal growth (SFSSCG) method exhibit relatively high dielectric loss. In order to reduce its dielectric loss, Cu, Bi and Mn co-doped KNN lead-free piezoelectric single crystals were prepared by the SFSSCG method. The effects of CuO doping content on the structure and electrical properties of (1-x)(0.996KNN-0.004BiMnO3)-xCuO crystals were systematically studied. The results show that doping proper amount of CuO is beneficial for the growth of the crystals and the improvement of electrical properties. When the diameter of the billets is 40 mm, the maximum crystal size of 25 × 21 × 2 mm3 are obtained. All crystals have a typical perovskite structure almost with a single orthorhombic phase, and are very compact almost without holes. The minimum average domain width of 276 nm is obtained for the crystal at x = 0.005. The KNN crystals exhibit a normal ferroelectric characteristics and space-charge-limited-conduction (SCLC) mechanism. The introduction of Cu2+ ions reduces the dielectric loss of the crystal and increases its piezoelectric and dielectric properties. The Cu, Bi and Mn co-doped KNN crystals achieve an excellent comprehensive properties: d33 = 314 pC/N, Pr = 29.9 μC/cm2, Ec = 10.1 kV/cm, d33* = 869 pm/V, Qm = 56.8, Kt = 0.38, tan δ = 0.013 and TC = 409 °C. This provides a route to improve the electrical properties of KNN-based crystals.
K0.5Na0.5NbO3(KNN)晶体具有优异的压电特性、高居里温度和环境友好性,因此具有广阔的应用前景。目前,通过无籽固态晶体生长(SFSSCG)方法生长的 KNN 晶体的介电损耗相对较高。为了降低介电损耗,采用 SFSSCG 方法制备了 Cu、Bi 和 Mn 共掺杂的 KNN 无铅压电单晶。系统研究了 CuO 掺杂量对 (1-x)(0.996KNN-0.004BiMnO3)-xCuO 晶体结构和电性能的影响。结果表明,掺入适量的 CuO 有利于晶体的生长和电性能的改善。当坯料直径为 40 毫米时,最大晶体尺寸为 25 × 21 × 2 立方毫米。所有晶体都具有典型的包晶结构,几乎是单一的正交相,而且非常紧凑,几乎没有空洞。x = 0.005 时,晶体的最小平均畴宽为 276 nm。KNN 晶体表现出正常的铁电特性和空间电荷限制传导(SCLC)机制。Cu2+ 离子的引入降低了晶体的介电损耗,增加了其压电和介电特性。Cu、Bi 和 Mn 共掺杂的 KNN 晶体具有出色的综合性能:d33 = 314 pC/N、Pr = 29.9 μC/cm2、Ec = 10.1 kV/cm、d33* = 869 pm/V、Qm = 56.8、Kt = 0.38、tan δ = 0.013 和 TC = 409 ℃。这为改善基于 KNN 晶体的电气性能提供了一条途径。
{"title":"Structure and electrical properties of Cu, Bi and Mn co-doped K0.5Na0.5NbO3 single crystals grown by seed-free solid state crystal growth method","authors":"Yuan Xu, Minhong Jiang, Xinkang Liu, Yujiao Zeng, Shixuan Cao, Yujiao Ouyang, Jianwei Song, Guang-Hui Rao","doi":"10.1039/d4ce00502c","DOIUrl":"https://doi.org/10.1039/d4ce00502c","url":null,"abstract":"K0.5Na0.5NbO3 (KNN) crystals have great application prospects due to their excellent piezoelectric properties, high Curie temperature, and environmental friendliness. Currently, KNN crystals grown by the seed-free solid-state crystal growth (SFSSCG) method exhibit relatively high dielectric loss. In order to reduce its dielectric loss, Cu, Bi and Mn co-doped KNN lead-free piezoelectric single crystals were prepared by the SFSSCG method. The effects of CuO doping content on the structure and electrical properties of (1-x)(0.996KNN-0.004BiMnO3)-xCuO crystals were systematically studied. The results show that doping proper amount of CuO is beneficial for the growth of the crystals and the improvement of electrical properties. When the diameter of the billets is 40 mm, the maximum crystal size of 25 × 21 × 2 mm3 are obtained. All crystals have a typical perovskite structure almost with a single orthorhombic phase, and are very compact almost without holes. The minimum average domain width of 276 nm is obtained for the crystal at x = 0.005. The KNN crystals exhibit a normal ferroelectric characteristics and space-charge-limited-conduction (SCLC) mechanism. The introduction of Cu2+ ions reduces the dielectric loss of the crystal and increases its piezoelectric and dielectric properties. The Cu, Bi and Mn co-doped KNN crystals achieve an excellent comprehensive properties: d33 = 314 pC/N, Pr = 29.9 μC/cm2, Ec = 10.1 kV/cm, d33* = 869 pm/V, Qm = 56.8, Kt = 0.38, tan δ = 0.013 and TC = 409 °C. This provides a route to improve the electrical properties of KNN-based crystals.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141611804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Role of Tetrel bonds in the Supramolecular Architecture of Tetranuclear Pb(II)[LL’Thiophene carboxylate] Complexes – An Experimental and Computational Study 四核 Pb(II)[LL'噻吩羧酸盐]配合物超分子结构中四键的作用--实验和计算研究
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1039/d4ce00466c
Swinton Darious Robert, Gifta Evangeline Henry, Franc Perdih, Angeline Vedha Swaminathan
This work explores the synthesis and DFT study of five tetranuclear Pb(II) complexes and the role of tetrel bonding in their crystal Engineering. Three synthesised Pb(II) complexes and Two theoretical tetrameric Pb(II) Complexes with Halogenated Thiophene carboxylate and 1, 10- Phenanthroline ligands are reported here. Their structural configurations, which feature chair-like repeating units connected via oxygen bridges, without Pb-Pb bonds, show two types of packing arrangements. Each Pb atoms form hemidirectional coordination creating space for the formation of tetrel bonds. The close packed arrangements are stabilised and guided by tetrel Bonds. The Pb...Br tetrel bonds were found to contribute -4.38 kcal/mol and Pb…Cl -3.37 Kcal/mol for the stability of the complexes. These terel bonds direct the packing arrangements within the crystal lattice. Additionally, Open packed arrangements are stabilised by hydrogen bonds. These findings offer new insights into the design of lead-based Metal Organic frameworks and highlights the critical role of tetrel bonds in the crystal architecture.
这项研究探讨了五种四核铅(II)配合物的合成和 DFT 研究,以及四键在其晶体工程中的作用。本文报告了三个合成的铅(II)配合物和两个理论上的四核铅(II)配合物,它们分别含有卤代噻吩羧酸盐和 1,10- 菲罗啉配体。它们的结构构型以通过氧桥连接的椅状重复单元为特征,没有 Pb-Pb 键,呈现出两种类型的堆积排列。每个铅原子形成半向配位,为形成四键创造了空间。紧密堆积排列由四键稳定和引导。在复合物的稳定性方面,Pb...Br 四键的贡献为 -4.38 kcal/mol,Pb...Cl 为 -3.37 Kcal/mol。这些四键引导了晶格内的堆积排列。此外,氢键也稳定了开放式堆积排列。这些发现为铅基金属有机框架的设计提供了新的见解,并强调了四键在晶体结构中的关键作用。
{"title":"Role of Tetrel bonds in the Supramolecular Architecture of Tetranuclear Pb(II)[LL’Thiophene carboxylate] Complexes – An Experimental and Computational Study","authors":"Swinton Darious Robert, Gifta Evangeline Henry, Franc Perdih, Angeline Vedha Swaminathan","doi":"10.1039/d4ce00466c","DOIUrl":"https://doi.org/10.1039/d4ce00466c","url":null,"abstract":"This work explores the synthesis and DFT study of five tetranuclear Pb(II) complexes and the role of tetrel bonding in their crystal Engineering. Three synthesised Pb(II) complexes and Two theoretical tetrameric Pb(II) Complexes with Halogenated Thiophene carboxylate and 1, 10- Phenanthroline ligands are reported here. Their structural configurations, which feature chair-like repeating units connected via oxygen bridges, without Pb-Pb bonds, show two types of packing arrangements. Each Pb atoms form hemidirectional coordination creating space for the formation of tetrel bonds. The close packed arrangements are stabilised and guided by tetrel Bonds. The Pb...Br tetrel bonds were found to contribute -4.38 kcal/mol and Pb…Cl -3.37 Kcal/mol for the stability of the complexes. These terel bonds direct the packing arrangements within the crystal lattice. Additionally, Open packed arrangements are stabilised by hydrogen bonds. These findings offer new insights into the design of lead-based Metal Organic frameworks and highlights the critical role of tetrel bonds in the crystal architecture.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141611691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Control of 3D oriented strain-induced natural rubber crystallites under spatial confinement: cellulose nanocrystal networks and thickness dependence 空间限制下三维定向应变诱导天然橡胶结晶的控制:纤维素纳米晶网络和厚度依赖性
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1039/d4ce00192c
Qiran Wang, Yingkun Song, QIngsong Zhang, Juqiao Su, Bin Liu, Lin Fu, Shouke Yan, Jian Hu
New insights into 3D-oriented strain-induced crystallization of natural rubber /cellulose nanocrystals (NR/CNCs) composites have been obtained by 2D wide-angle X-ray diffraction (2D-WAXD). Upon CNCs content exceeding 10 wt%, the mechanical behavior of the material exhibits a yield point that resembles those observed in plastics. Taking into account the influence of filler content of CNCs and thickness, the three-dimensional orientation degree of NR crystallites can be quantitatively assessed. The formation of 3D NR crystallites can be established when the CNCs content surpasses 10%, and concurrently, the degree of three-dimensional orientation of crystallites increases as thickness decreases. It was found that not only do CNCs enhance the confinement effect, leading to a decrease in the onset strain, but it is also beneficial for the formation of 3D-oriented strain-induced NR crystallites. The current study not only helps to a comprehensive understanding of the mechanism of 3D-oriented strain-induced NR crystallites by the constrained rigid filler network, but also provides the potential application of uniaxial tensile stretching in creating 3D functional materials.
通过二维广角 X 射线衍射(2D-WAXD),我们对天然橡胶/纤维素纳米晶体(NR/CNCs)复合材料的三维导向应变诱导结晶有了新的认识。当 CNCs 含量超过 10 wt% 时,材料的机械性能表现出与塑料类似的屈服点。考虑到 CNCs 填料含量和厚度的影响,可以定量评估 NR 晶粒的三维取向度。当 CNCs 含量超过 10%时,三维 NR 结晶的形成就可以确定;同时,随着厚度的减小,结晶的三维取向度也会增加。研究发现,CNCs 不仅能增强约束效应,从而降低起始应变,还有利于形成三维取向应变诱导的 NR 结晶体。目前的研究不仅有助于全面了解受约束刚性填料网络在三维方向应变诱导 NR 晶粒的机理,还为单轴拉伸在创建三维功能材料方面提供了潜在的应用。
{"title":"Control of 3D oriented strain-induced natural rubber crystallites under spatial confinement: cellulose nanocrystal networks and thickness dependence","authors":"Qiran Wang, Yingkun Song, QIngsong Zhang, Juqiao Su, Bin Liu, Lin Fu, Shouke Yan, Jian Hu","doi":"10.1039/d4ce00192c","DOIUrl":"https://doi.org/10.1039/d4ce00192c","url":null,"abstract":"New insights into 3D-oriented strain-induced crystallization of natural rubber /cellulose nanocrystals (NR/CNCs) composites have been obtained by 2D wide-angle X-ray diffraction (2D-WAXD). Upon CNCs content exceeding 10 wt%, the mechanical behavior of the material exhibits a yield point that resembles those observed in plastics. Taking into account the influence of filler content of CNCs and thickness, the three-dimensional orientation degree of NR crystallites can be quantitatively assessed. The formation of 3D NR crystallites can be established when the CNCs content surpasses 10%, and concurrently, the degree of three-dimensional orientation of crystallites increases as thickness decreases. It was found that not only do CNCs enhance the confinement effect, leading to a decrease in the onset strain, but it is also beneficial for the formation of 3D-oriented strain-induced NR crystallites. The current study not only helps to a comprehensive understanding of the mechanism of 3D-oriented strain-induced NR crystallites by the constrained rigid filler network, but also provides the potential application of uniaxial tensile stretching in creating 3D functional materials.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Bimetallic-atoms improved Ni3S2 bifunctional electrocatalysts for efficient hydrogen evolution reaction and overall water splitting performance 双金属原子改进型 Ni3S2 双功能电催化剂,可实现高效氢进化反应和整体水分离性能
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1039/d4ce00569d
Junjie Huang, Lan Mu, Yangyang Ou, Gang Zhao, Jinzhao Huang, Xiao Wang, Baojie Zhang
Hydrogen Evolution Reaction (HER), as a pivotal half-reaction, significantly hinders the advancement of energy conversion efficiency. Metal electrodeposition on catalysts has been demonstrated to effectively enhance the HER reactivity. Here, Ni3S2-Fe-Ni with multilayer structure was obtained by the electrodeposition of Ni3S2 with doped Fe/Ni, in which a number of active sites were achieved and intrinsic conductivity of the catalyst was well improved. Elemental analyses revealed the multilayer structure consisting of Ni3S2, NiS, and Fe. The Ni3S2-Fe-Ni catalyst exhibited impressive electrochemical performance due to optimization of its structure with the overpotential of HER and OER of only 83 and 190 mV. Notably, at higher current densities of 100 mA cm-2, the overpotential for HER and OER are only 339 and 365 mV. As a bifunctional electrocatalyst, its total splitting voltage was only 1.55V. The catalysis performance remained nearly unchanged after 48 h of stability testing. Finally, Density functional theory (DFT) calculations revealed that the potential barriers in each reaction step of the OER are evenly distributed, optimizing the Ni3S2 structure with iron and nickel atoms reduced the reaction energy barriers during the electrochemical process, improving the OER/HER performance.
氢气进化反应(HER)作为一种关键的半反应,极大地阻碍了能源转换效率的提高。在催化剂上进行金属电沉积已被证明能有效提高 HER 反应活性。本文通过电沉积掺杂铁/镍的 Ni3S2,获得了具有多层结构的 Ni3S2-Fe-Ni,其中存在多个活性位点,催化剂的本征导电性也得到了很好的改善。元素分析表明,催化剂具有由 Ni3S2、NiS 和 Fe 组成的多层结构。由于结构的优化,Ni3S2-Fe-Ni 催化剂表现出令人印象深刻的电化学性能,HER 和 OER 的过电位仅为 83 和 190 mV。值得注意的是,在 100 mA cm-2 的较高电流密度下,HER 和 OER 的过电位仅为 339 和 365 mV。作为一种双功能电催化剂,其总分裂电压仅为 1.55V。经过 48 小时的稳定性测试后,催化性能几乎保持不变。最后,密度泛函理论(DFT)计算表明,OER 各反应步骤的势垒分布均匀,优化含有铁原子和镍原子的 Ni3S2 结构可降低电化学过程中的反应能垒,从而提高 OER/HER 性能。
{"title":"Bimetallic-atoms improved Ni3S2 bifunctional electrocatalysts for efficient hydrogen evolution reaction and overall water splitting performance","authors":"Junjie Huang, Lan Mu, Yangyang Ou, Gang Zhao, Jinzhao Huang, Xiao Wang, Baojie Zhang","doi":"10.1039/d4ce00569d","DOIUrl":"https://doi.org/10.1039/d4ce00569d","url":null,"abstract":"Hydrogen Evolution Reaction (HER), as a pivotal half-reaction, significantly hinders the advancement of energy conversion efficiency. Metal electrodeposition on catalysts has been demonstrated to effectively enhance the HER reactivity. Here, Ni3S2-Fe-Ni with multilayer structure was obtained by the electrodeposition of Ni3S2 with doped Fe/Ni, in which a number of active sites were achieved and intrinsic conductivity of the catalyst was well improved. Elemental analyses revealed the multilayer structure consisting of Ni3S2, NiS, and Fe. The Ni3S2-Fe-Ni catalyst exhibited impressive electrochemical performance due to optimization of its structure with the overpotential of HER and OER of only 83 and 190 mV. Notably, at higher current densities of 100 mA cm-2, the overpotential for HER and OER are only 339 and 365 mV. As a bifunctional electrocatalyst, its total splitting voltage was only 1.55V. The catalysis performance remained nearly unchanged after 48 h of stability testing. Finally, Density functional theory (DFT) calculations revealed that the potential barriers in each reaction step of the OER are evenly distributed, optimizing the Ni3S2 structure with iron and nickel atoms reduced the reaction energy barriers during the electrochemical process, improving the OER/HER performance.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 and the Crystal Structure of a new 1D Metal–Organic Coordination Polymer with Cu2+ ions based on a Chiral Terephthalic Acid Derivative synthesized for the first time 基于首次合成的手性对苯二甲酸衍生物的含 Cu2+ 离子的新型一维金属有机配位聚合物的合成及其晶体结构
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1039/d4ce00408f
Vladimir V. Veselovsky, Vera Ilynichna Isaeva, Vera D Nissenbaum, Vladimir V. Chernyshev
The new homochiral 1D metal-organic coordination polymer {Cu[bdc-(N-MePro)H2O]•0.25H2O}n was synthesized starting from the 2-[(1-methyl-L-prolyl)amino]terephthalic acid obtained for the first time. The unique crystal structures of the new compounds were established by powder X-ray diffraction. The catalytic performance of {Cu[bdc-(N-MePro)H2O]•0.25H2O}n in the asymmetric ring opening reactions of styrene oxide and cyclohexene oxide with aniline was evaluated.
从首次获得的 2-[(1-甲基-L-脯氨酰)氨基]对苯二甲酸开始,合成了新的同手性一维金属有机配位聚合物 {Cu[bdc-(N-MePro)H2O]-0.25H2O}n。粉末 X 射线衍射确定了新化合物的独特晶体结构。评估了{Cu[bdc-(N-MePro)H2O]-0.25H2O}n 在氧化苯乙烯和氧化环己烯与苯胺的不对称开环反应中的催化性能。
{"title":"Synthesis and the Crystal Structure of a new 1D Metal–Organic Coordination Polymer with Cu2+ ions based on a Chiral Terephthalic Acid Derivative synthesized for the first time","authors":"Vladimir V. Veselovsky, Vera Ilynichna Isaeva, Vera D Nissenbaum, Vladimir V. Chernyshev","doi":"10.1039/d4ce00408f","DOIUrl":"https://doi.org/10.1039/d4ce00408f","url":null,"abstract":"The new homochiral 1D metal-organic coordination polymer {Cu[bdc-(N-MePro)H2O]•0.25H2O}n was synthesized starting from the 2-[(1-methyl-L-prolyl)amino]terephthalic acid obtained for the first time. The unique crystal structures of the new compounds were established by powder X-ray diffraction. The catalytic performance of {Cu[bdc-(N-MePro)H2O]•0.25H2O}n in the asymmetric ring opening reactions of styrene oxide and cyclohexene oxide with aniline was evaluated.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Syntheses, Structures and Luminescence of Several Coordination Complexes Based on -octamolybdate and Ag/Cu Phosphine Units 基于 -辛钼酸盐和 Ag/Cu 磷单元的几种配位配合物的合成、结构和发光特性
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1039/d4ce00496e
YI-Qi Yu, Shang-Bin Sun, Wen-Hao Deng, Jian Li, Zhi-Yi Lu, Jia-Hui He, Longsheng Wang, Xiang Gao Meng
Four new POMs-based coordination complexes [Cu(TPP)2(CH3CN)2]2{[Cu(TPP)2]2(-Mo8O26)}·2CH3CN (1) (TPP = Triphenylphosphine), {[Ag(TPP)]2·[Ag(TPP)2]2·(-Mo8O26)}·6DMF(2), {[Cu2(DPPM)2(CH3CN)]2(-Mo8O26)}·2CH3CN·2DCM (3) (DPPM = Bis(diphenylphosphino)methane), {[Ag2(DPPM)2∙(CH3CN)]2(-Mo8O26)}·2CH3CN·2DCM (4) were prepared through the self-assembly of α-octamolybdates and corresponding Cu/Ag phosphine building blocks. Single crystal X-ray diffraction reveals that compound 1 consist of two cations of [Cu(TPP)2(CH3CN)2]+ and one anion of {[Cu(TPP)2]2(-Mo8O26)}2-, the anion of {[Cu(TPP)2]2(-Mo8O26)}2- can be viewed that the central -Mo8O26 cluster are coordinated with two Cu(TPP)2 units via terminal oxygen atoms to form a linear trimer; compound 2 is a neutral cross-like pentamer which is made up of the central -Mo8O26 coordinated with two equatorial Ag(TPP)2 units and two Ag(TPP) units above and below the -Mo8O26 cluster via the terminal oxygen atoms; compounds 3 and 4 can be viewed as a trimer consisting of two binuclear copper clusters of {[Cu2(DPPM)2(CH3CN)]2}2+ or {[Ag2(DPPM)2(CH3CN)]2}2+ bridged by one -Mo8O26 anion cluster via terminal oxygen atoms. Their structures are further evidenced by FT-IR and PXRD. TGA study indicates that the skeleton of compounds 1 - 4 can stable up to 250 ~ 290°C and then followed a rapid weight loss. Their bond gaps can be calculated (Eg value: 2.27eV for 1, 3.14eV for 2, 2.66eV for 3, and 3.16eV for 4) using the Tauc’s method according to the solid state UV diffuse reflection spectra of compounds 1 - 4. Upon the irritation of the 211nm, compounds 1 - 4 exhibit a series of successive emissions around 360nm, 380nm and 400nm, which demonstrate a similar solid state emission compared to their corresponding Cu/Ag phosphine building blocks.
四种新的基于 POMs 的配位配合物 [Cu(TPP)2(CH3CN)2]2{[Cu(TPP)2]2(-Mo8O26)}-2CH3CN (1)(TPP = 三苯基膦)、{[Ag(TPP)]2-[Ag(TPP)2]2-(-Mo8O26)}-6DMF(2)、{[Cu2(DPPM)2(CH3CN)]2(-Mo8O26)}-2CH3CN-2DCM(3)(DPPM = 双(二苯基膦)甲烷)、{[Ag2(DPPM)2∙(CH3CN)]2(-Mo8O26)}-2CH3CN-2DCM(4)是通过α-八钼酸盐和相应的铜/银膦结构单元的自组装制备的。单晶 X 射线衍射显示,化合物 1 由[Cu(TPP)2(CH3CN)2]+ 的两个阳离子和{[Cu(TPP)2]2(-Mo8O26)}- 的一个阴离子组成,从{[Cu(TPP)2]2(-Mo8O26)}- 的阴离子可以看出,中心 -Mo8O26 簇通过末端氧原子与两个 Cu(TPP)2 单元配位,形成线性三聚体;化合物 2 是一种中性交叉样五聚体,由中心 -Mo8O26 通过末端氧原子与两个赤道 Ag(TPP)2 单元和 -Mo8O26 簇上下的两个 Ag(TPP) 单元配位组成;化合物 3 和 4 可视为由两个双核铜簇组成的三聚体,其中{[Cu2(DPPM)2(CH3CN)]2}2+ 或 {[Ag2(DPPM)2(CH3CN)]2}2+ 通过末端氧原子与一个 -Mo8O26 阴离子簇桥接。FT-IR 和 PXRD 进一步证明了它们的结构。TGA 研究表明,化合物 1 - 4 的骨架可在 250 ~ 290°C 的温度下保持稳定,然后迅速失重。根据化合物 1 - 4 的固态紫外漫反射光谱,可以用陶氏方法计算出它们的键隙(Eg 值:1 为 2.27eV,2 为 3.14eV,3 为 2.66eV,4 为 3.16eV)。在 211nm 波长的刺激下,化合物 1 - 4 在 360nm 波长、380nm 波长和 400nm 波长附近出现了一系列连续发射,与相应的铜/银膦结构单元相比,显示出类似的固态发射。
{"title":"Syntheses, Structures and Luminescence of Several Coordination Complexes Based on -octamolybdate and Ag/Cu Phosphine Units","authors":"YI-Qi Yu, Shang-Bin Sun, Wen-Hao Deng, Jian Li, Zhi-Yi Lu, Jia-Hui He, Longsheng Wang, Xiang Gao Meng","doi":"10.1039/d4ce00496e","DOIUrl":"https://doi.org/10.1039/d4ce00496e","url":null,"abstract":"Four new POMs-based coordination complexes [Cu(TPP)2(CH3CN)2]2{[Cu(TPP)2]2(-Mo8O26)}·2CH3CN (1) (TPP = Triphenylphosphine), {[Ag(TPP)]2·[Ag(TPP)2]2·(-Mo8O26)}·6DMF(2), {[Cu2(DPPM)2(CH3CN)]2(-Mo8O26)}·2CH3CN·2DCM (3) (DPPM = Bis(diphenylphosphino)methane), {[Ag2(DPPM)2∙(CH3CN)]2(-Mo8O26)}·2CH3CN·2DCM (4) were prepared through the self-assembly of α-octamolybdates and corresponding Cu/Ag phosphine building blocks. Single crystal X-ray diffraction reveals that compound 1 consist of two cations of [Cu(TPP)2(CH3CN)2]+ and one anion of {[Cu(TPP)2]2(-Mo8O26)}2-, the anion of {[Cu(TPP)2]2(-Mo8O26)}2- can be viewed that the central -Mo8O26 cluster are coordinated with two Cu(TPP)2 units via terminal oxygen atoms to form a linear trimer; compound 2 is a neutral cross-like pentamer which is made up of the central -Mo8O26 coordinated with two equatorial Ag(TPP)2 units and two Ag(TPP) units above and below the -Mo8O26 cluster via the terminal oxygen atoms; compounds 3 and 4 can be viewed as a trimer consisting of two binuclear copper clusters of {[Cu2(DPPM)2(CH3CN)]2}2+ or {[Ag2(DPPM)2(CH3CN)]2}2+ bridged by one -Mo8O26 anion cluster via terminal oxygen atoms. Their structures are further evidenced by FT-IR and PXRD. TGA study indicates that the skeleton of compounds 1 - 4 can stable up to 250 ~ 290°C and then followed a rapid weight loss. Their bond gaps can be calculated (Eg value: 2.27eV for 1, 3.14eV for 2, 2.66eV for 3, and 3.16eV for 4) using the Tauc’s method according to the solid state UV diffuse reflection spectra of compounds 1 - 4. Upon the irritation of the 211nm, compounds 1 - 4 exhibit a series of successive emissions around 360nm, 380nm and 400nm, which demonstrate a similar solid state emission compared to their corresponding Cu/Ag phosphine building blocks.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Controllable growth of large-size α-GeTe nanosheets with ferroelectricity by substrate pre-annealing 通过衬底预退火实现具有铁电性的大尺寸 α-GeTe 纳米片的可控生长
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1039/d4ce00499j
Zhaxi Suonan, Shuo Mi, Hanxiang Wu, Hua Xu, Haoyan Zhang, Shanshan Chen, Zhihai Cheng, Fei Pang
The atmospheric chemical vapor deposition (APCVD) method has been widely applied to synthesize high-quality two-dimensional materials. GeTe has many intriguing properties, such as phase transition, thermoelectric and ferroelectricity, which allows unique opportunities for functional ferroelectric devices. Here, we systematically investigated effects of various parameters during growth of α-GeTe nanosheets on mica by APCVD. The single crystals α-GeTe nanosheets possesses a lateral size of up to ≈30 µm and a thickness as low as ≈8.6 nm. It’s found substrate pre-annealing significantly impacts the nucleation density of α-GeTe nanosheets. Furthermore, the room temperature ferroelectric properties of α-GeTe nanosheets grown by CVD has been reported for the first time. This work offers an effective accessible method for controllable growth of large-size 2D α-GeTe to explore its fascinating multiferroic properties.
大气化学气相沉积(APCVD)方法已被广泛应用于合成高质量的二维材料。GeTe 具有许多引人入胜的特性,如相变、热电和铁电性,这为功能性铁电器件的发展提供了独特的机遇。在此,我们系统地研究了通过 APCVD 法在云母上生长 α-GeTe 纳米片时各种参数的影响。单晶 α-GeTe 纳米片的横向尺寸可达 ≈30 µm,厚度低至 ≈8.6 nm。研究发现,衬底预退火会显著影响α-GeTe 纳米片的成核密度。此外,首次报道了通过 CVD 法生长的 α-GeTe 纳米片的室温铁电特性。这项研究为大尺寸二维 α-GeTe 的可控生长提供了一种有效的方法,以探索其迷人的多铁电特性。
{"title":"Controllable growth of large-size α-GeTe nanosheets with ferroelectricity by substrate pre-annealing","authors":"Zhaxi Suonan, Shuo Mi, Hanxiang Wu, Hua Xu, Haoyan Zhang, Shanshan Chen, Zhihai Cheng, Fei Pang","doi":"10.1039/d4ce00499j","DOIUrl":"https://doi.org/10.1039/d4ce00499j","url":null,"abstract":"The atmospheric chemical vapor deposition (APCVD) method has been widely applied to synthesize high-quality two-dimensional materials. GeTe has many intriguing properties, such as phase transition, thermoelectric and ferroelectricity, which allows unique opportunities for functional ferroelectric devices. Here, we systematically investigated effects of various parameters during growth of α-GeTe nanosheets on mica by APCVD. The single crystals α-GeTe nanosheets possesses a lateral size of up to ≈30 µm and a thickness as low as ≈8.6 nm. It’s found substrate pre-annealing significantly impacts the nucleation density of α-GeTe nanosheets. Furthermore, the room temperature ferroelectric properties of α-GeTe nanosheets grown by CVD has been reported for the first time. This work offers an effective accessible method for controllable growth of large-size 2D α-GeTe to explore its fascinating multiferroic properties.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Evaluation of halogen bonding proclivity of oxazole derivatives carrying multiple acceptor sites in cocrystals with perfluorinated iodobenzenes 评估全氟碘苯共晶体中携带多个受体位点的噁唑衍生物的卤键亲和性
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-10 DOI: 10.1039/d4ce00557k
Ruđer Sušanj, Nikola Bedekovic, Sara Cerovski, Nea Baus Topić, Vinko Nemec, Dominik Cinčić
In order to study the competition between halogen bond acceptor sites of multifunctional N,O,X-based halogen bond acceptors (X = S, O, N or π aromatic ring) we have synthesized a family of oxazole derivatives and cocrystallized them with selected iodoperfluorinated benzenes as halogen bond donors. Out of 28 combinations, 19 experiments yielded crystals suitable for single-crystal X-ray diffraction. Structural analysis revealed that in all of the obtained cocrystals the most prominent supramolecular interaction is the I···Noxazole halogen bond with relative shortening values of up to 18 %, comparable to I···Npyridine halogen bond shortening values. The acceptors are ditopic in 10 cocrystals and form additional I···N, I···O or I··· π halogen bonds. A majority of cocrystals feature one donor molecule per one acceptor molecule. In order to rank the acceptor sites and establish how the electrostatic potential differences impact the supramolecular landscape around these molecules, the values of molecular electrostatic potentials (MEPs) were calculated on their optimized geometries. These calculations were in agreement with experimental observations, since the best (most negative MEP value) acceptor binding site in the series of used oxazoles is the oxazole nitrogen atom. Depending on the difference between MEP values of the oxazole oxygen atom and the peripheral functionalities, additional halogen bonds could potentially be formed with one of these acceptor sites, leading to the formation of two different types of halogen-bonded supramolecular chains.
为了研究基于 N、O、X 的多功能卤键受体(X = S、O、N 或 π 芳环)的卤键受体位点之间的竞争,我们合成了一系列噁唑衍生物,并将它们与选定的碘全氟苯作为卤键供体进行了共晶体化。在 28 种组合中,19 次实验得到了适合单晶 X 射线衍射的晶体。结构分析表明,在所有获得的共晶体中,最突出的超分子相互作用是I--Noxazole卤素键,其相对缩短值高达18%,与I--Npyridine卤素键缩短值相当。在 10 种共晶中,受体是二配位的,并形成额外的 I--N、I--O 或 I--- π 卤素键。大多数共晶体都是一个供体分子对一个受体分子。为了对受体位点进行排序,并确定静电位差如何影响这些分子周围的超分子景观,我们计算了这些分子优化几何结构的分子静电位(MEP)值。这些计算结果与实验观察结果一致,因为在所用的恶唑系列中,恶唑氮原子是最佳(MEP 值最负)的受体结合位点。根据噁唑氧原子和外围官能团的 MEP 值之间的差异,有可能与其中一个受体位点形成额外的卤素键,从而形成两种不同类型的卤素键超分子链。
{"title":"Evaluation of halogen bonding proclivity of oxazole derivatives carrying multiple acceptor sites in cocrystals with perfluorinated iodobenzenes","authors":"Ruđer Sušanj, Nikola Bedekovic, Sara Cerovski, Nea Baus Topić, Vinko Nemec, Dominik Cinčić","doi":"10.1039/d4ce00557k","DOIUrl":"https://doi.org/10.1039/d4ce00557k","url":null,"abstract":"In order to study the competition between halogen bond acceptor sites of multifunctional N,O,X-based halogen bond acceptors (X = S, O, N or π aromatic ring) we have synthesized a family of oxazole derivatives and cocrystallized them with selected iodoperfluorinated benzenes as halogen bond donors. Out of 28 combinations, 19 experiments yielded crystals suitable for single-crystal X-ray diffraction. Structural analysis revealed that in all of the obtained cocrystals the most prominent supramolecular interaction is the I···Noxazole halogen bond with relative shortening values of up to 18 %, comparable to I···Npyridine halogen bond shortening values. The acceptors are ditopic in 10 cocrystals and form additional I···N, I···O or I··· π halogen bonds. A majority of cocrystals feature one donor molecule per one acceptor molecule. In order to rank the acceptor sites and establish how the electrostatic potential differences impact the supramolecular landscape around these molecules, the values of molecular electrostatic potentials (MEPs) were calculated on their optimized geometries. These calculations were in agreement with experimental observations, since the best (most negative MEP value) acceptor binding site in the series of used oxazoles is the oxazole nitrogen atom. Depending on the difference between MEP values of the oxazole oxygen atom and the peripheral functionalities, additional halogen bonds could potentially be formed with one of these acceptor sites, leading to the formation of two different types of halogen-bonded supramolecular chains.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141570174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Construction of high-performance flexible hybrid capacitor at extreme work temperature (-20 oC) 在极端工作温度(-20 oC)下构建高性能柔性混合电容器
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-09 DOI: 10.1039/d4ce00628c
Xingjie Sun, Xiang Wu, Lixian Sun
Designing electrode materials with special core-shell structure are one of great significance to improve the performance of supercapacitors. In this work, we fabricate several kinds of ZnCo2S4@Ni(OH)2 composite electrodes through a multistep hydrothermal strategy. ZnCo2S4 nanowire clusters grow uniformly on nickel foam substrate. They are covered with Ni(OH)2 nanosheets to form a core-shell structure. Three-dimensional structured composite expose many active sites and shorten the ions transport path. The as-obtained electrode material presents a specific capacity of 1262.1 C g-1 at 1 A g-1. It still maintains 81% of the initial capacity after 20000 times cycling at 10 A g-1. The ZnCo2S4@Ni(OH)2//AC delivers an energy density of 127.5 Wh kg-1 when the power density reaches to 2700 W kg-1. The devices possess an exceptional mechanical stability after repeated folding from 0 º to 180 º. In addition, it maintains initial capacitance of 68% after 2500 cycles at 3 A g-1 even when the operating temperature decreases to -20 °C.
设计具有特殊核壳结构的电极材料对于提高超级电容器的性能具有重要意义。在这项工作中,我们通过多步水热策略制备了多种 ZnCo2S4@Ni(OH)2 复合电极。ZnCo2S4 纳米线簇均匀地生长在泡沫镍基底上。它们被 Ni(OH)2 纳米片覆盖,形成核壳结构。三维结构的复合材料暴露了许多活性位点,缩短了离子传输路径。获得的电极材料在 1 A g-1 时的比容量为 1262.1 C g-1。在 10 A g-1 下循环 20000 次后,它仍能保持 81% 的初始容量。当功率密度达到 2700 W kg-1 时,ZnCo2S4@Ni(OH)2//AC 的能量密度为 127.5 Wh kg-1。在从 0 º 到 180 º 的反复折叠过程中,该器件具有出色的机械稳定性。此外,即使工作温度降至 -20 °C,在 3 A g-1 条件下循环 2500 次后,它仍能保持 68% 的初始电容。
{"title":"Construction of high-performance flexible hybrid capacitor at extreme work temperature (-20 oC)","authors":"Xingjie Sun, Xiang Wu, Lixian Sun","doi":"10.1039/d4ce00628c","DOIUrl":"https://doi.org/10.1039/d4ce00628c","url":null,"abstract":"Designing electrode materials with special core-shell structure are one of great significance to improve the performance of supercapacitors. In this work, we fabricate several kinds of ZnCo2S4@Ni(OH)2 composite electrodes through a multistep hydrothermal strategy. ZnCo2S4 nanowire clusters grow uniformly on nickel foam substrate. They are covered with Ni(OH)2 nanosheets to form a core-shell structure. Three-dimensional structured composite expose many active sites and shorten the ions transport path. The as-obtained electrode material presents a specific capacity of 1262.1 C g-1 at 1 A g-1. It still maintains 81% of the initial capacity after 20000 times cycling at 10 A g-1. The ZnCo2S4@Ni(OH)2//AC delivers an energy density of 127.5 Wh kg-1 when the power density reaches to 2700 W kg-1. The devices possess an exceptional mechanical stability after repeated folding from 0 º to 180 º. In addition, it maintains initial capacitance of 68% after 2500 cycles at 3 A g-1 even when the operating temperature decreases to -20 °C.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141570035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Influence of the Crystallisation Solution Environment on the Structural Pathway from Solute Solvation to the Polymorphic Forms of Tolfenamic Acid 结晶溶液环境对olfenamic Acid 从溶质溶解到多晶型结构途径的影响
IF 3.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-09 DOI: 10.1039/d4ce00460d
Yu Liu, Cai Yun Ma, Junbo Gong, Kevin John Roberts
The influence of the solution environment on the solution crystallisation of the conformational polymorphic forms I and II of tolfenamic acid is assessed through integration of multi-scale (molecular, cluster and crystallographic) modelling with polymorphic screening using polythermal crystallisation as a function of solvent selection. Solid-state analysis reveals the contrasting crystal chemistry with the strongest synthon involving hydrogen bonding synthons and π – π van der Waals interactions for forms I and II, respectively. Analysis of the molecular conformational energies reveals the molecular structures for forms I and II to be very close which is matched by their calculated lattice energies. Crystallisation as a function of both solute concentration and solution cooling rate reveals form II to be mostly more preferred than form I. The higher stability of the form II conformer together with its easier conformational adjustment during the formation of form II crystals, is consistent with its greater crystallisability compared to the more stable form I. Solute concentration analysis of the relative stabilities of the two forms as a function of their sizes reveals that smaller cluster sizes, are required to stabilise the crystal structure for form I with respect to form II. Polymorphic screening as a function of solvent confirms the predicted poor crystallisability of form I whose crystallisation is preferred at higher initial solute concentrations and lower cooling rates in polar solvents but less so for the more apolar solvent toluene, the latter being consistent with π – π solute/solvent interactions promoting the formation of hydrogen bonded solute/solute synthons at the expense of π – π interactions. Modelling work correlates well with the observed crystallisation behaviour, highlighting the importance of understanding solvent selection and solution state structure at the molecular-scale level for directing polymorphic outcomes as confirmed by the higher crystallisability of the metastable form II.
通过将多尺度(分子、团簇和晶体学)建模与多态筛选相结合,利用多热结晶作为溶剂选择的函数,评估了溶液环境对构象多态形式 I 和 II 托非那酸的溶液结晶的影响。固态分析揭示了对比强烈的晶体化学性质,I 型和 II 型的最强合子分别涉及氢键合子和 π - π 范德瓦耳斯相互作用。分子构象能分析表明,形态 I 和形态 II 的分子结构非常接近,这与它们的计算晶格能相吻合。根据溶质浓度和溶液冷却速度对两种形态的相对稳定性进行的分析表明,相对于形态 I,形态 II 需要较小的簇尺寸才能稳定晶体结构。随溶剂变化而进行的多态性筛选证实了形式 I 结晶性较差的预测,在极性溶剂中,较高的初始溶质浓度和较低的冷却速率更有利于形式 I 的结晶,但在非极性溶剂甲苯中则不那么有利,后者与 π - π 溶质/溶剂相互作用促进形成氢键溶质/固形物合子而牺牲 π - π 相互作用是一致的。建模工作与观察到的结晶行为有很好的相关性,突出了在分子尺度水平上理解溶剂选择和溶液状态结构对于指导多晶型结果的重要性,这一点已被 "蜕变形式 II "的较高结晶性所证实。
{"title":"Influence of the Crystallisation Solution Environment on the Structural Pathway from Solute Solvation to the Polymorphic Forms of Tolfenamic Acid","authors":"Yu Liu, Cai Yun Ma, Junbo Gong, Kevin John Roberts","doi":"10.1039/d4ce00460d","DOIUrl":"https://doi.org/10.1039/d4ce00460d","url":null,"abstract":"The influence of the solution environment on the solution crystallisation of the conformational polymorphic forms I and II of tolfenamic acid is assessed through integration of multi-scale (molecular, cluster and crystallographic) modelling with polymorphic screening using polythermal crystallisation as a function of solvent selection. Solid-state analysis reveals the contrasting crystal chemistry with the strongest synthon involving hydrogen bonding synthons and π – π van der Waals interactions for forms I and II, respectively. Analysis of the molecular conformational energies reveals the molecular structures for forms I and II to be very close which is matched by their calculated lattice energies. Crystallisation as a function of both solute concentration and solution cooling rate reveals form II to be mostly more preferred than form I. The higher stability of the form II conformer together with its easier conformational adjustment during the formation of form II crystals, is consistent with its greater crystallisability compared to the more stable form I. Solute concentration analysis of the relative stabilities of the two forms as a function of their sizes reveals that smaller cluster sizes, are required to stabilise the crystal structure for form I with respect to form II. Polymorphic screening as a function of solvent confirms the predicted poor crystallisability of form I whose crystallisation is preferred at higher initial solute concentrations and lower cooling rates in polar solvents but less so for the more apolar solvent toluene, the latter being consistent with π – π solute/solvent interactions promoting the formation of hydrogen bonded solute/solute synthons at the expense of π – π interactions. Modelling work correlates well with the observed crystallisation behaviour, highlighting the importance of understanding solvent selection and solution state structure at the molecular-scale level for directing polymorphic outcomes as confirmed by the higher crystallisability of the metastable form II.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141570385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
期刊
CrystEngComm
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1