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Tuning of Anomalous Hall Effect by Systematic Doping on Mn3Sn 通过在 Mn3Sn 上系统掺杂调谐反常霍尔效应
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-17 DOI: 10.1021/acs.cgd.4c00104
Rikizo Yano, Taichi Kabeya, Masahiro Hayashi, Shunya Kihara, Hiroyuki Suto, Kenji Yoshida, Takeo Yamaguchi, Satoshi Kashiwaya
Mn3Sn is an AHE antiferromagnet exhibiting a hysteretic anomalous Hall effect (AHE) originating from the cluster octupole moments of inverse triangular antiferromagnetic spins at room temperature, whereas the AHE disappears at low temperatures. In this study, we evaluated the systematic doping effect on the AHE of Mn3Sn to stabilize the AHE at low temperatures. We grew single crystals of M0.1Mn2.9Sn and Mn3Sn0.9X0.1 (M = Cr and Fe; X = Si and Ge) and evaluated their transport and magnetic properties. Compared with doping at the Sn site, doping at the Mn site drastically changes the AHE at low temperatures. Reproducible magnetic structures were not observed at low temperatures owing to low Fe content fluctuation near x ∼ 0.1 in FexMn3–xSn. Some crystals showed a large hysteretic-type AHE, unlike the AHE at 300 K, while others did not show a finite AHE below 50 K. Conversely, Cr doping stabilizes the AHE with additional magnetoresistance that hinders observing the AHE. Considering these features, we prepared Cr and Fe codoped Mn3Sn crystals. The Fe0.05/Cr0.1-doped Mn3Sn crystals showed the AHE from room temperature to 2 K without magnetic transitions. This finding provides a new route to access octupole-driven phenomena of Mn3Sn-based devices at low temperatures.
Mn3Sn 是一种 AHE 反铁磁体,在室温下表现出源于反三角反铁磁自旋的簇八极矩的滞后反常霍尔效应(AHE),而在低温下 AHE 消失。在本研究中,我们评估了系统掺杂对 Mn3Sn 的 AHE 的影响,以稳定低温下的 AHE。我们生长了 M0.1Mn2.9Sn 和 Mn3Sn0.9X0.1(M = Cr 和 Fe;X = Si 和 Ge)的单晶体,并评估了它们的传输和磁性能。与在锡位点掺杂相比,在锰位点掺杂会极大地改变低温下的 AHE。由于 FexMn3-xSn 中的铁含量在 x ∼ 0.1 附近波动较小,因此在低温下无法观察到可再现的磁性结构。一些晶体显示出与 300 K 时的 AHE 不同的大滞后型 AHE,而另一些晶体在 50 K 以下则没有显示出有限的 AHE。考虑到这些特点,我们制备了掺杂铬和铁的 Mn3Sn 晶体。掺杂了 Fe0.05/Cr0.1 的 Mn3Sn 晶体从室温到 2 K 都显示出了无磁转变的 AHE。这一发现为在低温下获得基于 Mn3Sn 器件的八极驱动现象提供了一条新途径。
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引用次数: 0
Supramolecular Catalysis of a Halogen-Bonded Co-crystal that Undergoes a [2 + 2] Cycloaddition Reaction Formed via Dry Vortex Grinding 通过干式涡流研磨形成的发生 [2 + 2] 环化反应的卤键共晶体的超分子催化作用
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-17 DOI: 10.1021/acs.cgd.4c00738
Jaelin Holdaway, Eric Bosch, Daniel K. Unruh, Ryan H. Groeneman
The ability to achieve a catalytic [2 + 2] cycloaddition reaction involving trans-1,2-bis(4-pyridyl)ethylene (BPE) within a halogen-bonded cocrystal formed via a dry vortex grinding approach is reported. The donor, namely 1,4-diiodoperchlorobenzene (C6I2Cl4), behaves as a catalytic supramolecular template at both substoichiometric and stoichiometric ratios to achieve a nearly quantitative photoreaction in the organic solid state. The mechanochemical grinding not only generates the initial photoreactive cocrystal (C6I2Cl4)·(BPE) but subsequently facilitates dynamic turnover that releases the photoproduct rctt-tetrakis(4-pyridyl)cyclobutane (TPCB) and regenerates the reactive cocrystal. Importantly, additional grinding–photolysis sequences increase the yield, which ultimately returns a near quantitative value for the solid-state cycloaddition reaction. Lastly, this dry vortex grinding approach also increases the yield for the photoreaction previously reported for the cocrystal (C6I2Cl4)·(BPE) formed from a stoichiometric ratio of the components. After photoreaction, the resulting equal molar solid is ground a second time and exposed to ultraviolet light to increase the yield to a near quantitative level matching that for the substoichiometric solid.
据报道,在通过干式涡旋研磨方法形成的卤素键合晶体中,能够实现涉及反式-1,2-双(4-吡啶基)乙烯(BPE)的催化[2 + 2]环加成反应。供体,即 1,4-二碘过氯苯(C6I2Cl4),在亚化学计量比和化学计量比两种情况下都可作为催化超分子模板,在有机固态中实现近乎定量的光反应。机械化学研磨不仅产生了初始光反应共晶体 (C6I2Cl4)-(BPE),而且随后促进了动态周转,释放出光反应产物 rctt-四(4-吡啶基)环丁烷 (TPCB),并使反应共晶体再生。重要的是,额外的研磨-光解顺序提高了产率,最终使固态环化反应接近定量值。最后,这种干式涡旋研磨方法还提高了之前报道的由各组分的化学计量比形成的共晶体 (C6I2Cl4)-(BPE) 的光反应产率。光反应结束后,对得到的等摩尔固体进行第二次研磨,并将其暴露在紫外线下,以提高产率,使其接近亚几何固体的定量水平。
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引用次数: 0
Ab Initio Discovery of Group IV–V Monolayers with Superlative Mechanical, Electronic, and Transport Properties 具有超级机械、电子和传输特性的 IV-V 族单层的 Ab Initio 发现
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-17 DOI: 10.1021/acs.cgd.4c00643
Kang Sheng, Zhi-Yong Wang
Much effort has been made to discover new two-dimensional semiconductors with exotic properties for exciting applications. Herein, we predict a class of group IV–V monolayers by first-principles calculations with chemical stoichiometry α′-MIVXV (M = C, Si, Ge, Sn, Pb; X = N, P, As, Sb, Bi), which consist of four sublayers in the M-X-X-M rather than the earlier extensively reported X-M-M-X stacking sequence. Among these 25 allotropes, we identify that 19 combinations hold great possibility to be realized in experiments by securing their robust bonding, energetic, dynamical, thermal, and mechanical stabilities. Electronic band structures reveal that except for 3 metallic materials verified by the HSE06 hybrid functional in the presence of the spin–orbit coupling (SOC) effect, the remaining 16 monolayers are intrinsic semiconductors due to the absence of surface dangling bonds, whose direct or indirect bandgaps range from 0.01 to 1.23 eV at the PBE + SOC level. Also, it is found that all of these semiconductors exhibit a pair of inequivalent K valleys in the conduction and valence bands. The strong SOC effect in semiconductors made up of heavy elements leads to the remarkable valley spin splitting in the absence of inversion symmetry. The robust spin-valley locking can not only realize the coexistence of spin and valley Hall effects but also achieve fascinating valley polarization by the irradiation of circularly polarized infrared light. The ultrahigh ultimate tensile strengths endow these semiconducting systems with superior tailored properties. Their considerable and anisotropic mobilities facilitate fast carrier transportation and exciton separation efficiency. Overall, these appealing properties along with viable synthesizability will provide semiconducting α′-MIVXV monolayers with tremendous opportunities in a broad variety of potential applications.
人们一直在努力发现具有奇特性质的新型二维半导体,以实现令人兴奋的应用。在这里,我们通过第一原理计算预测了一类 IV-V 族单层化合物,其化学计量为 α′-MIVXV(M = C、Si、Ge、Sn、Pb;X = N、P、As、Sb、Bi),由 M-X-X-M 而不是早先广泛报道的 X-M-M-X 堆积序列中的四个子层组成。在这 25 种同素异形体中,我们发现有 19 种组合具有很强的成键、能量、动力学、热和机械稳定性,因此很有可能在实验中实现。电子能带结构显示,除了 3 种在存在自旋轨道耦合(SOC)效应的情况下通过 HSE06 混合函数验证的金属材料外,其余 16 种单层材料由于不存在表面悬空键而成为本征半导体,其直接或间接带隙在 PBE + SOC 水平上介于 0.01 至 1.23 eV 之间。此外,研究还发现所有这些半导体在导带和价带中都表现出一对不等价的 K 谷。由重元素组成的半导体中强烈的 SOC 效应导致在没有反转对称性的情况下出现显著的谷自旋分裂。强大的自旋-谷锁定不仅能实现自旋和谷霍尔效应的共存,还能通过圆偏振红外光的照射实现迷人的谷极化。超高的极限拉伸强度赋予了这些半导体系统卓越的定制特性。它们相当大的各向异性迁移率促进了载流子的快速运输和激子分离效率。总之,这些吸引人的特性以及可行的合成能力将为半导体 α′-MIVXV 单层在各种潜在应用中提供巨大的机会。
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引用次数: 0
Revealing the Solubility Enhancement of Active Pharmaceutical Ingredients through Eutectic Mixtures Formation: A Parameter Study 通过共晶混合物的形成提高活性药物成分的溶解度:参数研究
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-13 DOI: 10.1021/acs.cgd.4c00617
Sahar Nasrallah, Ahmad Alhadid, Mirjana Minceva
The active pharmaceutical ingredient (API) solubility is critical for their bioavailability, dosing precision, stability, and overall efficacy. Forming eutectic mixtures between an API and an excipient has been widely used to improve API solubility. However, from a thermodynamic perspective, this approach is still relatively underexplored. This study explores the parameters influencing the solubility enhancement of an API with poor solubility in water by eutectic mixture formation. A hypothetical ternary system consisting of an API, excipient, and water was considered. The study investigated the impact of excipient melting properties and molecular interactions among the API, excipient, and water on API solubility in water. The two-suffix Margules equation was used to model the liquid phase nonideality. The study revealed that strong API–excipient and excipient–water interactions notably enhanced API solubility in water. However, this effect was counteracted when excipient–water interactions surpassed API–excipient interactions in strength. Additionally, the melting properties of the excipient had a significant influence on the composition of the mixture at the eutectic point and API solubility enhancement factor. This research underscores the essential characteristics a potential excipient should possess to maximize API solubility in water and other solvents. The results emphasize the importance of eutectic mixture formation in addressing the challenges associated with water-insoluble APIs.
活性药物成分(API)的溶解度对其生物利用度、剂量精度、稳定性和整体疗效至关重要。在原料药和辅料之间形成共晶混合物已被广泛用于提高原料药的溶解度。然而,从热力学的角度来看,对这种方法的探索还相对不足。本研究探讨了通过共晶混合物的形成提高在水中溶解度较差的原料药溶解度的影响参数。研究考虑了一个由原料药、辅料和水组成的假定三元体系。研究调查了辅料的熔融特性以及原料药、辅料和水之间的分子相互作用对原料药在水中溶解度的影响。该研究采用了双ffix Margules方程来模拟液相非理想性。研究结果表明,原料药-赋形剂和赋形剂-水之间的强烈相互作用显著提高了原料药在水中的溶解度。然而,当赋形剂与水的相互作用强度超过原料药与赋形剂的相互作用强度时,这种效应就会被抵消。此外,辅料的熔化特性对共晶点的混合物成分和原料药溶解度增强因子也有显著影响。这项研究强调了潜在辅料应具备的基本特性,以最大限度地提高原料药在水和其他溶剂中的溶解度。研究结果强调了共晶混合物的形成在应对与水不溶性原料药相关的挑战方面的重要性。
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引用次数: 0
Syntheses, Crystal Structures, and Luminescence of Hexafluoroacetylacetone Dinuclear Lanthanide Complexes Bridged by “Back-to-Back” Bisterpyridine 六氟乙酰丙酮双核镧系配合物的合成、晶体结构和发光特性--以 "背对背 "比斯特吡啶为桥
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acs.cgd.4c00306
Yan Li, Yi-Fan Liu, Cheng-Long Yu, Sheng-Mei Zhang, Kai Wang
Six dinuclear lanthanide complexes [(hfac)3Ln(μ-tppz)Ln(hfac)3] [Ln(III) = 1-Eu, 2-Gd, 3-Tb, hfac = 1,1,1,5,5,5-hexafluoroacetylacetone, tppz = 2,3,5,6-tetra(pyridin-2-yl)pyrazine], [(hfac)3Ln(μ-tppz)Ln(hfac)3]·CH2Cl2 [Ln(III) = 4-Dy, 5-Yb, 6-Er], and seven dinuclear lanthanide complexes [(hfac)3Ln(μ-1,4-bteb)Nd(hfac)3] [Ln(III) = 7-Nd, 1,4-bteb = 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene] and [(hfac)3Ln(μ-1,4-bteb)Ln(hfac)3]·2CH2Cl2 [Ln(III) = 8-Sm, 9-Eu, 10-Gd, 11-Td, 12-Dy, 13-Yb], were synthesized and characterized by elemental analyses, infrared spectroscopy, thermogravimetric analyses, single-crystal X-ray diffraction, and powder X-ray diffraction. Solid-state luminescence investigations suggest that an efficient energy transfer process is taking place in 1-Eu and 9-Eu. The dominant intersystem crossing (ISC) and the ligand-to-metal energy transfer (ET) processes in the dinuclear Eu(III) complex bridged by tppz are more efficient, making 1-Eu possess longer τ and higher quantum yield (QY) (0.687 ms and 53.47%) than 9-Eu (0.670 ms and 14.22%). Additionally, the mononuclear complex [Eu(NO3)3(ptpy)(H2O)] shows longer τ and higher QY (0.545 ms and 16.80%) than the dinuclear complex [Eu(NO3)3(H2O)]2(μ-tppz) (0.035 ms and 1.31%) and [Eu(hfac)3(ptpy)] has longer τ and higher QY (0.819 ms and 59.95%) than 9-Eu. The results imply that increasing the length of the “back-to-back” bisterpyridine ligands or the number of the Eu(III) centers could make the luminescence performances such as τ and QY decrease. There is an inefficient energy transfer existing in the Tb(III) and Dy(III) complexes because of the back energy transfer (BET) processes, which leads to an unfavorable condition in observing significantly the characteristic Tb(III)- and Dy(III)-based emissions. However, the synergistic effect of hfac and tppz (or hfac and 1,4-bteb) could sensitize the visible and near-infrared (NIR) luminescence of Sm(III) ion and the NIR luminescence of Nd(III), Er(III), and Yb(III) ions. The τ value and the calculated intrinsic quantum yield (ϕLn) of 7-Nd are 1.13 μs and 0.13%, respectively. This work unveils the synergistic sensitization effect of primary hfac ligands and the ancillary tppz and 1,4-bteb ligands and the influences of the length of the bridging bisterpyridine ligands and the numbers of the Ln(III) centers on the luminescence properties. It is anticipated that the synthesized dual-sensitized ternary lanthanide complexes might be excellent candidates for some optoelectronic applications.
六种双核镧系配合物[(hfac)3Ln(μ-tppz)Ln(hfac)3][Ln(III) = 1-Eu、2-Gd、3-Tb,hfac = 1,1,1,5,5,5-六氟乙酰丙酮,tppz = 2,3,5,6-四(吡啶-2-基)吡嗪]、(hfac)3Ln(μ-tppz)Ln(hfac)3]-CH2Cl2[Ln(III) = 4-Dy、5-Yb、6-Er],以及 7 个双核镧系配合物[(hfac)3Ln(μ-1,4-bteb)Nd(hfac)3][Ln(III) = 7-Nd,1,4-bteb = 1,4-双(2,2′:6′,2″-terpyridin-4′-yl)benzene] 和 [(hfac)3Ln(μ-1,4-bteb)Ln(hfac)3]-2CH2Cl2[Ln(III) = 8-Sm、9-Eu、10-Gd、11-Td、12-Dy、13-Yb]、的合成,并通过元素分析、红外光谱、热重分析、单晶 X 射线衍射和粉末 X 射线衍射对其进行了表征。固态发光研究表明,1-Eu 和 9-Eu 发生了高效的能量转移过程。在以 tppz 为桥的双核 Eu(III)配合物中,占主导地位的系统间交叉(ISC)和配体到金属的能量转移(ET)过程更为有效,这使得 1-Eu 比 9-Eu(0.670 毫秒和 14.22%)具有更长的τ 和更高的量子产率(QY)(0.687 毫秒和 53.47%)。此外,单核配合物[Eu(NO3)3(ptpy)(H2O)]比双核配合物[Eu(NO3)3(H2O)]2(μ-tppz)(0.035 ms 和 1.31%)显示出更长的 τ 和更高的 QY(0.545 ms 和 16.80%),而[Eu(hfac)3(ptpy)]比 9-Eu 显示出更长的 τ 和更高的 QY(0.819 ms 和 59.95%)。这些结果表明,增加 "背靠背 "双胞吡啶配体的长度或 Eu(III)中心的数量会降低发光性能,如 τ 和 QY。由于反向能量转移(BET)过程,Tb(III) 和 Dy(III) 复合物中的能量转移效率较低,这导致在观察基于 Tb(III) 和 Dy(III) 的特征发射时处于不利条件。然而,hfac 和 tppz(或 hfac 和 1,4-镱)的协同效应可以敏化 Sm(III)离子的可见光和近红外(NIR)发光以及 Nd(III)、Er(III)和 Yb(III)离子的近红外发光。7-Nd 的 τ 值和计算出的本征量子产率 (ϕLn) 分别为 1.13 μs 和 0.13%。这项工作揭示了主 hfac 配体与辅助 tppz 和 1,4-bteb 配体的协同增敏效应,以及桥接双isterpyridine 配体的长度和 Ln(III) 中心的数量对发光特性的影响。预计合成的双敏化三元镧系配合物可能会成为某些光电应用的理想候选材料。
{"title":"Syntheses, Crystal Structures, and Luminescence of Hexafluoroacetylacetone Dinuclear Lanthanide Complexes Bridged by “Back-to-Back” Bisterpyridine","authors":"Yan Li, Yi-Fan Liu, Cheng-Long Yu, Sheng-Mei Zhang, Kai Wang","doi":"10.1021/acs.cgd.4c00306","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00306","url":null,"abstract":"Six dinuclear lanthanide complexes [(hfac)<sub>3</sub>Ln(μ-tppz)Ln(hfac)<sub>3</sub>] [Ln(III) = <b>1</b>-Eu, <b>2</b>-Gd, <b>3</b>-Tb, hfac = 1,1,1,5,5,5-hexafluoroacetylacetone, tppz = 2,3,5,6-tetra(pyridin-2-yl)pyrazine], [(hfac)<sub>3</sub>Ln(μ-tppz)Ln(hfac)<sub>3</sub>]·CH<sub>2</sub>Cl<sub>2</sub> [Ln(III) = <b>4</b>-Dy, <b>5</b>-Yb, <b>6</b>-Er], and seven dinuclear lanthanide complexes [(hfac)<sub>3</sub>Ln(μ-1,4-bteb)Nd(hfac)<sub>3</sub>] [Ln(III) = <b>7</b>-Nd, 1,4-bteb = 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene] and [(hfac)<sub>3</sub>Ln(μ-1,4-bteb)Ln(hfac)<sub>3</sub>]·2CH<sub>2</sub>Cl<sub>2</sub> [Ln(III) = <b>8</b>-Sm, <b>9</b>-Eu, <b>10</b>-Gd, <b>11</b>-Td, <b>12</b>-Dy, <b>13</b>-Yb], were synthesized and characterized by elemental analyses, infrared spectroscopy, thermogravimetric analyses, single-crystal X-ray diffraction, and powder X-ray diffraction. Solid-state luminescence investigations suggest that an efficient energy transfer process is taking place in <b>1</b>-Eu and <b>9</b>-Eu. The dominant intersystem crossing (ISC) and the ligand-to-metal energy transfer (ET) processes in the dinuclear Eu(III) complex bridged by tppz are more efficient, making <b>1</b>-Eu possess longer τ and higher quantum yield (QY) (0.687 ms and 53.47%) than <b>9</b>-Eu (0.670 ms and 14.22%). Additionally, the mononuclear complex [Eu(NO<sub>3</sub>)<sub>3</sub>(ptpy)(H<sub>2</sub>O)] shows longer τ and higher QY (0.545 ms and 16.80%) than the dinuclear complex [Eu(NO<sub>3</sub>)<sub>3</sub>(H<sub>2</sub>O)]<sub>2</sub>(μ-tppz) (0.035 ms and 1.31%) and [Eu(hfac)<sub>3</sub>(ptpy)] has longer τ and higher QY (0.819 ms and 59.95%) than <b>9</b>-Eu. The results imply that increasing the length of the “back-to-back” bisterpyridine ligands or the number of the Eu(III) centers could make the luminescence performances such as τ and QY decrease. There is an inefficient energy transfer existing in the Tb(III) and Dy(III) complexes because of the back energy transfer (BET) processes, which leads to an unfavorable condition in observing significantly the characteristic Tb(III)- and Dy(III)-based emissions. However, the synergistic effect of hfac and tppz (or hfac and 1,4-bteb) could sensitize the visible and near-infrared (NIR) luminescence of Sm(III) ion and the NIR luminescence of Nd(III), Er(III), and Yb(III) ions. The τ value and the calculated intrinsic quantum yield (ϕ<sub>Ln</sub>) of <b>7</b>-Nd are 1.13 μs and 0.13%, respectively. This work unveils the synergistic sensitization effect of primary hfac ligands and the ancillary tppz and 1,4-bteb ligands and the influences of the length of the bridging bisterpyridine ligands and the numbers of the Ln(III) centers on the luminescence properties. It is anticipated that the synthesized dual-sensitized ternary lanthanide complexes might be excellent candidates for some optoelectronic applications.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613212","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 Cambridge Structural Database Study of Pancake Bonding and Geometry in Dithiadiazolyls 剑桥结构数据库对二噻二唑中饼状键合和几何形状的研究
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1021/acs.cgd.4c00596
Marisa Strydom, Delia A. Haynes
A comprehensive study of 1,2,3,5-dithiadiazolyls (DTDAs) in the Cambridge Structural Database (CSD) has been carried out. The effect of both charge on the S–N ring and pancake bonding on the geometry of these heterocycles in the solid state has been investigated. Particular attention was given to changes in the S–S bond length in the thiazyl ring with changes in oxidation state or dimerization. Trends identified in the CSD data allowed for the definitive identification of partially anionic −CNSSN rings in crystal structures in the CSD. A computational study of two simple DTDA derivatives confirms the general observations from the CSD study and reveals the importance of substituent effects in these systems.
我们对剑桥结构数据库(CSD)中的 1,2,3,5-二噻二唑(DTDA)进行了全面研究。研究了 S-N 环上的电荷和薄饼键对这些杂环在固态下几何形状的影响。我们特别关注了噻嗪环中 S-S 键长度随氧化态或二聚化变化而发生的变化。在 CSD 数据中发现的趋势使我们能够在 CSD 晶体结构中确定部分阴离子 -CNSSN 环。对两种简单 DTDA 衍生物的计算研究证实了 CSD 研究的一般观察结果,并揭示了取代基效应在这些体系中的重要性。
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引用次数: 0
Kinetics of Calcite Nucleation onto Sulfated Chitosan Derivatives and Implications for Water–Polysaccharide Interactions during Crystallization of Sparingly Soluble Salts 硫酸化壳聚糖衍生物上方解石成核动力学及其对难溶盐结晶过程中水与多糖相互作用的影响
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1021/acs.cgd.4c00602
Brenna M. Knight, Ronnie Mondal, Nizhou Han, Nicholas F. Pietra, Brady A. Hall, Kevin J. Edgar, Valerie Vaissier Welborn, Louis A. Madsen, James J. De Yoreo, Patricia M. Dove
Anionic macromolecules are found at sites of CaCO3 biomineralization in diverse organisms, but their roles in crystallization are not well-understood. We prepared a series of sulfated chitosan derivatives with varied positions and degrees of sulfation, DS(SO3), and measured calcite nucleation rate onto these materials. Fitting the classical nucleation theory model to the kinetic data reveals the interfacial free energy of the calcite–polysaccharide–solution system, γnet, is lowest for nonsulfated controls and increases with DS(SO3). The kinetic prefactor also increases with DS(SO3). Simulations of Ca2+–H2O–chitosan systems show greater water structuring around sulfate groups compared to uncharged substituents, independent of sulfate location. Ca2+–SO3 interactions are solvent-separated by distances that are inversely correlated with DS(SO3) of the polysaccharide. The simulations also predict SO3 and NH3+ groups affect the solvation waters and HCO3 ions associated with Ca2+. Integrating the experimental and computational evidence suggests sulfate groups influence nucleation by increasing the difficulty of displacing near-surface water, thereby increasing γnet. By correlating γnet and net charge per monosaccharide for diverse polysaccharides, we suggest the solvent-separated interactions of functional groups with Ca2+ influence thermodynamic and kinetic components to crystallization by similar solvent-dominated processes. The findings reiterate the importance of establishing water structure and properties at macromolecule–solution interfaces.
阴离子大分子存在于各种生物的 CaCO3 生物矿化部位,但它们在结晶过程中的作用还不十分清楚。我们制备了一系列不同硫化位置和硫化程度的硫酸化壳聚糖衍生物 DS(SO3-),并测量了这些材料上的方解石成核率。将经典成核理论模型与动力学数据拟合后发现,钙钛矿-多糖-溶液体系的界面自由能γnet在非硫酸化对照组中最低,并随 DS(SO3-) 的增加而增加。动力学前因子也随着 DS(SO3-) 的增加而增加。对 Ca2+-H2O 壳聚糖体系的模拟显示,与不带电的取代基相比,硫酸基团周围的水结构化程度更高,这与硫酸位置无关。Ca2+-SO3- 相互作用的溶解分离距离与多糖的 DS(SO3-) 成反比。模拟还预测 SO3- 和 NH3+ 基团会影响溶解水和与 Ca2+ 相关的 HCO3- 离子。综合实验和计算证据表明,硫酸基团通过增加近表面水置换的难度来影响成核,从而增加γnet。通过对不同多糖的γnet 和每个单糖的净电荷进行相关分析,我们发现官能团与 Ca2+ 的溶剂分离相互作用会通过类似的溶剂主导过程影响结晶的热力学和动力学成分。这些发现重申了在大分子-溶液界面建立水结构和特性的重要性。
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引用次数: 0
Structural Diversity and Catalytic Properties of Coordination Polymers with Functionalized Naphthalene Dicarboxylate Linkers 具有功能化萘二甲酸酯连接体的配位聚合物的结构多样性和催化特性
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-10 DOI: 10.1021/acs.cgd.4c00594
Xiuqi Kang, Zhenzhong Mei, Hongyu Wang, Jinzhong Gu, Jijun Xue, Mohammad Azam
Ten novel transition-metal-based coordination polymers were hydrothermally synthesized using metal salts (M = Co(II), Mn(II), Ni(II), and Zn(II)) with the primary ligand 4-aminonaphthalene-2,6-dicarboxylic acid (H2anda) as well as auxiliary ligands (phen: 1,10-phenanthroline; 2,2′-bipy: 2,2′-bipyridine; 4,4′-bipy: 4,4′-bipyridine; bpa: bis(4-pyridyl)amine, dpe: 1,2-di(4-pyridyl)ethylene or py: pyridine). The successful synthesis provided four two-dimensional (2D) and six three-dimensional (3D) coordination polymers, formulated as [Co(μ5-anda)(H2O)]n (1), [Co2(μ-anda)(μ4-anda)(phen)2]n (2), [M(μ4-anda)(phen)]n (M = Co (3), Mn (4)), [Co34-anda)3(2,2′-bipy)2]n (5), [Ni2(μ-anda)(μ4-anda)(μ-4,4′-bipy)2]n (6), [Co(μ-anda)(μ-bpa)]n·nH2O (7), [Mn64-anda)6(μ-dpe)3]n·22nH2O (8), and [M6(μ-anda)24-anda)(μ5-anda)(μ3-OH)4(py)2]n·2nH2O (M = Co (9), Zn (10)). A thorough investigation was conducted using conventional methods to look at the topological types and catalytic activity of the synthesized coordination polymers. Notably, under ideal conditions, coordination polymer 7 produced good conversion in the Henry and Knoevenagel condensation of benzaldehydes, demonstrating stability, high efficacy, and recyclability as a heterogeneous catalyst.
利用金属盐(M = Co(II)、Mn(II)、Ni(II)和 Zn(II))与主配体 4-氨基萘-2,6-二羧酸(H2anda)以及辅助配体(phen:1,10-菲罗啉;2,2′-联吡:2,2′-联吡啶;4,4′-联吡:4,4′-联吡啶:4,4′-联吡啶;bpa:双(4-吡啶基)胺;dpe:1,2-二(4-吡啶基)胺:1,2-二(4-吡啶基)乙烯或 py:吡啶)。成功合成的四种二维(2D)和六种三维(3D)配位聚合物分别为[Co(μ5-anda)(H2O)]n (1)、[Co2(μ-anda)(μ4-anda)(phen)2]n (2)、[M(μ4-anda)(phen)]n (M = Co (3)、Mn (4))、[Co3(μ4-anda)3(2,2′-bipy)2]n (5)、[Ni2(μ-anda)(μ4-anda)(μ-4,4′-bipy)2]n (6)、[Co(μ-anda)(μ-bpa)]n-nH2O (7)、[Mn6(μ4-anda)6(μ-dpe)3]n-22nH2O(8)和[M6(μ-anda)2(μ4-anda)(μ5-anda)(μ3-OH)4(py)2]n-2nH2O(M = Co (9),Zn (10))。我们采用传统方法对合成配位聚合物的拓扑类型和催化活性进行了深入研究。值得注意的是,在理想条件下,配位聚合物 7 在苯甲醛的 Henry 缩合和 Knoevenagel 缩合中产生了良好的转化率,显示了其作为异相催化剂的稳定性、高效性和可回收性。
{"title":"Structural Diversity and Catalytic Properties of Coordination Polymers with Functionalized Naphthalene Dicarboxylate Linkers","authors":"Xiuqi Kang, Zhenzhong Mei, Hongyu Wang, Jinzhong Gu, Jijun Xue, Mohammad Azam","doi":"10.1021/acs.cgd.4c00594","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00594","url":null,"abstract":"Ten novel transition-metal-based coordination polymers were hydrothermally synthesized using metal salts (M = Co(II), Mn(II), Ni(II), and Zn(II)) with the primary ligand 4-aminonaphthalene-2,6-dicarboxylic acid (H<sub>2</sub>anda) as well as auxiliary ligands (phen: 1,10-phenanthroline; 2,2′-bipy: 2,2′-bipyridine; 4,4′-bipy: 4,4′-bipyridine; bpa: bis(4-pyridyl)amine, dpe: 1,2-di(4-pyridyl)ethylene or py: pyridine). The successful synthesis provided four two-dimensional (2D) and six three-dimensional (3D) coordination polymers, formulated as [Co(μ<sub>5</sub>-anda)(H<sub>2</sub>O)]<sub><i>n</i></sub> (<b>1</b>), [Co<sub>2</sub>(μ-anda)(μ<sub>4</sub>-anda)(phen)<sub>2</sub>]<sub><i>n</i></sub> (<b>2</b>), [M(μ<sub>4</sub>-anda)(phen)]<sub><i>n</i></sub> (M = Co (<b>3</b>), Mn (<b>4</b>)), [Co<sub>3</sub>(μ<sub>4</sub>-anda)<sub>3</sub>(2,2′-bipy)<sub>2</sub>]<sub><i>n</i></sub> (<b>5</b>), [Ni<sub>2</sub>(μ-anda)(μ<sub>4</sub>-anda)(μ-4,4′-bipy)<sub>2</sub>]<sub><i>n</i></sub> (<b>6</b>), [Co(μ-anda)(μ-bpa)]<sub><i>n</i></sub>·<i>n</i>H<sub>2</sub>O (<b>7</b>), [Mn<sub>6</sub>(μ<sub>4</sub>-anda)<sub>6</sub>(μ-dpe)<sub>3</sub>]<sub><i>n</i></sub>·22<i>n</i>H<sub>2</sub>O (<b>8</b>), and [M<sub>6</sub>(μ-anda)<sub>2</sub>(μ<sub>4</sub>-anda)(μ<sub>5</sub>-anda)(μ<sub>3</sub>-OH)<sub>4</sub>(py)<sub>2</sub>]<sub><i>n</i></sub>·2<i>n</i>H<sub>2</sub>O (M = Co (<b>9</b>), Zn (<b>10</b>)). A thorough investigation was conducted using conventional methods to look at the topological types and catalytic activity of the synthesized coordination polymers. Notably, under ideal conditions, coordination polymer <b>7</b> produced good conversion in the Henry and Knoevenagel condensation of benzaldehydes, demonstrating stability, high efficacy, and recyclability as a heterogeneous catalyst.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613214","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
Mechanisms of Flow-Induced Multistep Structure Evolution in Semicrystalline Polymers Revealed by Molecular Simulations 分子模拟揭示半结晶聚合物中流动诱导多步结构演变的机理
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-10 DOI: 10.1021/acs.cgd.4c00592
Yijing Nie, Jianlong Wen, Yongqiang Ming, Yuhang Zhou
Research on polymer crystallization induced by flow has been one of the most fascinating topics in the field of polymer science. Structural changes during polymer crystallization induced by flow follow a multiscale and multistep mechanism. However, the structural changes are complex and rapid, making it challenging to accurately observe them online in experiments. Fortunately, computer molecular simulations provide a solution by allowing us to obtain detailed information about the microstructures at different stages and scales. This enables the simulation results to provide more accurate and comprehensive explanations of the microscopic mechanisms of flow-induced crystallization. In this Review, we delve into flow-induced microstructural evolutions, including conformational transition, segmental orientation, precursor formation, and shish formation, based on the results of molecular simulations. We also discuss the mechanisms of polymer nucleation induced by flow, including the formation mechanism of precursors, nucleation mode, the respective functions of chains with different lengths, the effect of nanofillers, and the effect of entanglements. Finally, we outline the future directions for simulation work on flow-induced crystallization. This includes the need for further investigation of the effects of entanglements on local segment orientation and precursor formation as well as the development of models capable of simulating the crystallization of different polymer materials. We also anticipate that the methods related to artificial intelligence, such as machine learning or deep learning, will play a significant role in constructing complex nonlinear relationships between the crystalline structure and mechanical properties.
有关流动诱导聚合物结晶的研究一直是聚合物科学领域最引人入胜的课题之一。流动诱导聚合物结晶过程中的结构变化遵循多尺度和多步骤机制。然而,结构变化既复杂又迅速,因此在实验中在线精确观测这些变化具有挑战性。幸运的是,计算机分子模拟提供了一种解决方案,使我们能够获得不同阶段和尺度上微观结构的详细信息。这使得模拟结果能够更准确、更全面地解释流动诱导结晶的微观机制。在本综述中,我们将根据分子模拟的结果深入探讨流动诱导的微观结构演变,包括构象转变、段取向、前体形成和菱形形成。我们还讨论了流动诱导聚合物成核的机制,包括前驱体的形成机制、成核模式、不同长度链的各自功能、纳米填料的影响以及缠结的影响。最后,我们概述了流动诱导结晶模拟工作的未来方向。这包括需要进一步研究缠结对局部链段取向和前驱体形成的影响,以及开发能够模拟不同聚合物材料结晶的模型。我们还预计,机器学习或深度学习等人工智能相关方法将在构建结晶结构与机械性能之间复杂的非线性关系方面发挥重要作用。
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引用次数: 0
Improved Quality of InN Thin Films Using a Thin InGaN Compressive Strain Gradient Layer 利用薄 InGaN 压缩应变梯度层提高 InN 薄膜质量
IF 3.8 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-09 DOI: 10.1021/acs.cgd.4c00095
Satish Shetty, Andrian V. Kuchuk, Fernando Maia de Oliveira, Serhii Kryvyi, Chen Li, Paul Minor, Mohammad Zamani-Alavijeh, Nirosh M. Eldose, Subhashis Das, Dinesh Baral, Yuriy I. Mazur, H. Alan Mantooth, Gregory J. Salamo
High-quality InN has significant opportunities for exciting and impactful electronic and photonic applications. These applications rely on growth techniques that produce high-quality InN thin films. To achieve the fabrication of InN semiconductor thin films with a low density of misfit and threading dislocations, we report on a growth technique that utilizes composition and strain gradients to limit the propagation of defects into InN grown on a GaN/sapphire substrate. The growth technique we have investigated utilizes a compressively strained gradient transition layer to limit the propagation of threading dislocations from the GaN buffer. Reflection high-energy electron diffraction, high-resolution X-ray diffraction, Raman spectroscopy, photoluminescence, and Hall measurements were employed to evaluate the effectiveness of the gradient transition layer to improve the quality of InN thin films. The outcome is that for InN films grown on partially graded InxGa1–xN (x → 0 to 29%), when compared with InN grown directly on a GaN substrate, we observed about a 40% decrease in edge dislocations, a 50% increase in photoluminescence, and a 20% increase in mobility. When compared to a sharp strain boundary, a linear strain gradient offers threading dislocations the opportunity to reduce the energy of the system more by leaving the system than by propagating into the strained region.
高质量的铟和氮化镓在电子和光子应用中有着令人兴奋和影响深远的重大机遇。这些应用依赖于能生产出高质量 InN 薄膜的生长技术。为了制造具有低错位和穿线位错密度的氮化铟半导体薄膜,我们报告了一种生长技术,它利用成分和应变梯度来限制生长在氮化镓/蓝宝石衬底上的氮化铟的缺陷传播。我们研究的生长技术利用压缩应变梯度过渡层来限制穿线位错从氮化镓缓冲区的传播。我们利用反射高能电子衍射、高分辨率 X 射线衍射、拉曼光谱、光致发光和霍尔测量来评估梯度过渡层在提高 InN 薄膜质量方面的有效性。结果表明,对于生长在部分梯度 InxGa1-xN (x → 0 至 29%)上的 InN 薄膜,与直接生长在 GaN 衬底上的 InN 相比,我们观察到边缘位错减少了约 40%,光致发光增加了 50%,迁移率增加了 20%。与尖锐的应变边界相比,线性应变梯度为穿线位错提供了机会,使其更多地通过离开系统而不是传播到应变区域来降低系统能量。
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引用次数: 0
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Crystal Growth & Design
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