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Electrosynthesis of Ammonia from Nitrate Using a Self-Activated Carbon Fiber Paper. 使用自激活碳纤维纸从硝酸盐电合成氨。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1021/acs.inorgchem.4c02353
Sai Zhang, Mengheng Dou, Mengdi Liu, Jianjian Yi, Min Chen, Limin Wu

While electrochemically upcycling nitrate wastes to valuable ammonia is considered a very promising pathway for tackling the environmental and energy challenges underlying the nitrogen cycle, the effective catalysts involved are mainly limited to metal-based materials. Here, we report that commercial carbon fiber paper, which is a classical current collector and is typically assumed to be electrochemically inert, can be significantly activated during the reaction. As a result, it shows a high NH3 Faradaic efficiency of 87.39% at an industrial-level current density of 300 mA cm-2 for over 90 h of continuous operation, with a NH3 production rate of as high as 1.22 mmol cm-2 h-1. Through experimental and theoretical analysis, the in situ-formed oxygen functional groups are demonstrated to be responsible for the NO3RR performance. Among them, the C-O-C group is finally identified as the active center, which lowers the thermodynamic energy barrier and simultaneously improves the hydrogenation kinetics. Moreover, high-purity NH4Cl and NH3·H2O were obtained by coupling the NO3RR with an air-stripping approach, providing an effective way for converting nitrate waste into high-value-added NH3 products.

虽然通过电化学方法将硝酸盐废料升级循环为有价值的氨气被认为是解决氮循环所带来的环境和能源挑战的一条非常有前景的途径,但其中涉及的有效催化剂主要局限于金属基材料。在这里,我们报告了商用碳纤维纸,它是一种经典的电流收集器,通常被认为是电化学惰性的,但在反应过程中可以被显著激活。因此,在 300 mA cm-2 的工业级电流密度下,连续运行 90 小时以上,它的 NH3 法拉第效率高达 87.39%,NH3 生成率高达 1.22 mmol cm-2 h-1。通过实验和理论分析,证明了原位形成的氧官能团是 NO3RR 性能的主要原因。其中,C-O-C 基团最终被确定为活性中心,它降低了热力学能垒,同时改善了氢化动力学。此外,通过将 NO3RR 与空气剥离方法耦合,还获得了高纯度的 NH4Cl 和 NH3-H2O,为将硝酸盐废料转化为高附加值的 NH3 产品提供了有效途径。
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引用次数: 0
Unraveling the Geometry-Driven C═C Epoxidation and C-H Hydroxylation Reactivity of Tetra-Coordinated Nonheme Iron(IV)-Oxo Complexes. 揭示四配位非heme Iron(IV)-Oxo Complexes 的几何驱动的 C═C 环氧化和 C-H 羟基化反应活性。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1021/acs.inorgchem.4c01708
Akhil Bhardwaj, Bhaskar Mondal

The electronic structure and reactivity of tetra-coordinated nonheme iron(IV)-oxo complexes have remained unexplored for years. The recent synthesis of a closed-shell iron(IV)-oxo complex [(quinisox)FeIV(O)]+ (1) has set up a platform to understand how such complexes compare with the celebrated open-shell iron-oxo chemistry. Herein, using density functional theory and ab initio calculations, we present an in-depth electronic structure investigation of the C═C epoxidation [oxygen atom transfer (OAT)] and C-H hydroxylation [hydrogen atom transfer (HAT)] reactivity of 1. Using a solvent-coordinated geometry of 1 (1') and other potential tetra-coordinated iron(IV)-oxo complexes bearing rigid ligands (2 and 3), we established the geometric origin of spin-state energetics and reactivity of 1. Complex 1 featuring a strong Fe-O bond exhibits OAT and HAT reactivity in its quintet state. The lowest quintet OAT pathway has a lower barrier by ∼4 kcal/mol than the quintet HAT pathway, corroborating the experimentally observed gas-phase OAT reactivity preference. A conventional HAT reactivity preference for 2 and a comparable OAT and HAT reactivity for 3 are observed. This further supports the geometry-driven reactivity preference for 1. Noncovalent interaction analyses reveal a pronounced π-π interaction between the substrate and ligand in the OAT transition state, rationalizing the origin of the observed reactivity preference for 1.

多年来,四配位非血红素铁(IV)-氧配合物的电子结构和反应性一直未得到研究。最近合成的闭壳铁(IV)-氧络合物[(quinisox)FeIV(O)]+ (1) 为了解此类络合物与著名的开壳铁-氧化学性质的比较提供了一个平台。在此,我们利用密度泛函理论和 ab initio 计算,对 1 的 C═C环氧化反应[氧原子转移(OAT)]和 C-H 羟基化反应[氢原子转移(HAT)]进行了深入的电子结构研究。利用 1 的溶剂配位几何结构(1')和其他带有刚性配体的潜在四配位铁(IV)-氧配合物(2 和 3),我们确定了 1 的自旋态能量和反应活性的几何来源。最低五元OAT途径比五元HAT途径的势垒低4 kcal/mol,证实了实验观察到的气相OAT反应性偏好。观察到 2 具有传统的 HAT 反应性偏好,而 3 具有类似的 OAT 和 HAT 反应性。这进一步支持了 1 的几何驱动反应性偏好。非共价相互作用分析表明,在 OAT 过渡态中,底物和配体之间存在明显的 π-π 相互作用,从而合理解释了所观察到的 1 的反应性偏好。
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引用次数: 0
Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity. Co3O4 装饰碳化硅棒上的强电场和 H2O 解离作用可实现 100%选择性光驱动 CO2 甲烷化。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1021/acs.inorgchem.4c01944
Min Lin, Qing Cai, Zhen Xiao, Hui Chen, Bing Wang, Chengwei Qiu, Jinni Shen, Jinlin Long, Wenxin Dai, Shitong Han, Xuxu Wang, Zizhong Zhang, Hailing Xi

Solar-driven methanation of carbon dioxide (CO2) with water (H2O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO2 was often hindered by the sluggish kinetics and the multiple competition of other C1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co3O4/SiC catalyst. The substantial difference in work functions between SiC and Co3O4 served as a significant source of the charge driving force, facilitating the conversion of CO2 to CH4. The high-valent cobalt Co(IV) in Co3O4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO2 methanation. DFT calculation showed that the energy barrier of CO2 hydrogenation was significantly reduced at the Co3O4/SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH4. The optimum CH4 evolution rate of Co3O4/SiC samples was 21.3 μmol g-1 h-1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO2 to CH4 products in photocatalysis applications.

太阳能驱动的二氧化碳(CO2)与水(H2O)的甲烷化已成为实现碳中和与燃料生产的重要策略。二氧化碳的选择性甲烷化往往受到缓慢的动力学和其他 C1 副产品的多重竞争的阻碍。为了克服这一瓶颈,我们利用生物质合成法合成了 SiC 棒,然后构建了一种直接 Z 型异质结 Co3O4/SiC 催化剂。SiC 和 Co3O4 之间功函数的巨大差异成为电荷驱动力的重要来源,促进了 CO2 向 CH4 的转化。Co3O4 中的高价钴 Co(IV)是促进水有效解离的活性物种。这一有利条件大大提高了催化剂表面单个位点周围电子和质子高浓度聚集的可能性,从而促进 CO2 甲烷化。DFT 计算表明,Co3O4/SiC 异质结界面上 CO2 加氢的能垒显著降低,从而改变了反应途径,使产物从 CO 完全转化为 CH4。Co3O4/SiC 样品的最佳 CH4 进化速率为 21.3 μmol g-1 h-1,选择性为 100%。该研究对于光催化应用中二氧化碳到 CH4 产物的选择性调节具有重要的指导意义。
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引用次数: 0
N,C,N-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties. 铂双金属配合物中的 N,C,N-钳:钳配体和桥配体对金属-金属键和光物理性质的影响。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1021/acs.inorgchem.4c01712
Miguel A Esteruelas, Sonia Moreno-Blázquez, Montserrat Oliván, Enrique Oñate

Precursors PtCl{κ3-N,C,N-[py-C6HMe2-py]} (1), PtCl{κ3-N,C,N-[py-O-C6H3-O-py]} (2), Pt(OH){κ3-N,C,N-[py-C6HMe2-py]} (3), and Pt(OH){κ3-N,C,N-[py-O-C6H3-O-py]} (4) were used to prepare d8-platinum bimetallic complexes. Precursors 1 and 2 react with AgBF4 and 7-azaindole (Haz) to give [Pt{κ3-N,C,N-[py-C6HMe2-py]}{κ1-N-[Haz]}]BF4 (5) and [Pt{κ3-N,C,N-[py-O-C6H3-O-py]}{κ1-N-[Haz]}]BF4 (6) and 3 and 4 with indolo[2,3-b]indole (H2ii) to generate Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-C6HMe2-py]} (7) and Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-O-C6H3-O-py]} (8). Subsequent addition of 3 and 4 to 5-7 affords bimetallic derivatives [{Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[az]}]BF4 (9), [{Pt[κ3-N,C,N-(py-O-C6H3-O-py)]}2{μ-N,N-[az]}]BF4 (10), and {Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[ii]} (11). X-ray structures of 9-11 reveal separations between the metals in sequence 9 (3.0515(4) Å) < 10 (3.2689(9) Å) < 11 (3.2949(2) Å). DFT calculations support σ overlap of the dz2 orbitals of platinum atoms, for 9 and 10. Accordingly, their absorption spectra show a MMLCT transition. Complex 9 is a red emitter. The excited state has 3MMLCT characteristics and a Pt-Pt separation of 2.763 Å. Complex 11 is a dual emitter in the red and NIR regions, in solid. Both excited states have a 3LC/LMCT characteristic and platinum-platinum separations of 3.290 and 3.202 Å. Intermediate 5 is a green emitter that achieves quantum yields close to unity, when diluted in PMMA and 1,2-dichloroethane at low concentrations.

前驱体 PtCl{κ3-N,C,N-[py-C6HMe2-py]} (1)、PtCl{κ3-N,C,N-[py-O-C6H3-O-py]} (2)、Pt(OH){κ3-N,C,N-[py-C6HMe2-py]} (3) 和 Pt(OH){κ3-N,C,N-[py-O-C6H3-O-py]} (4) 被用来制备 d8-铂双金属配合物。前体 1 和 2 与 AgBF4 和 7-azaindole (Haz) 反应,得到 [Pt{κ3-N,C,N-[py-C6HMe2-py]}{κ1-N-[Haz]}]BF4 (5) 和 [Pt{κ3-N,C、N-[py-O-C6H3-O-phy]}{κ1-N-[Haz]}]BF4 (6) 以及 3 和 4 与吲哚并[2,3-b]吲哚 (H2ii) 反应生成 Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-C6HMe2-py]} (7) 和 Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-O-C6H3-O-py]} (8)。随后将 3 和 4 加入 5-7 中,得到双金属衍生物[{Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[az]}]BF4 (9)、[{Pt[κ3-N,C,N-(py-O-C6H3-O-py)]}2{μ-N,N-[az]}]BF4(10),以及{Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[ii]}(11)。9-11 的 X 射线结构显示,金属之间的间隔依次为 9 (3.0515(4) Å) < 10 (3.2689(9) Å) < 11 (3.2949(2) Å)。DFT 计算支持 9 和 10 中铂原子 dz2 轨道的 σ 重叠。因此,它们的吸收光谱显示出 MMLCT 转变。配合物 9 是一种红色发射体。激发态具有 3MMLCT 特性,铂-铂分离度为 2.763 Å。中间体 5 是一种绿色发射体,在 PMMA 和 1,2-二氯乙烷中以低浓度稀释时,其量子产率接近于 1。
{"title":"<i>N,C,N</i>-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties.","authors":"Miguel A Esteruelas, Sonia Moreno-Blázquez, Montserrat Oliván, Enrique Oñate","doi":"10.1021/acs.inorgchem.4c01712","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01712","url":null,"abstract":"<p><p>Precursors PtCl{κ<sup>3</sup>-<i>N,C,N</i>-[py-C<sub>6</sub>HMe<sub>2</sub>-py]} (<b>1</b>), PtCl{κ<sup>3</sup>-<i>N,C,N</i>-[py-O-C<sub>6</sub>H<sub>3</sub>-O-py]} (<b>2</b>), Pt(OH){κ<sup>3</sup>-<i>N,C,N</i>-[py-C<sub>6</sub>HMe<sub>2</sub>-py]} (<b>3</b>), and Pt(OH){κ<sup>3</sup>-<i>N,C,N</i>-[py-O-C<sub>6</sub>H<sub>3</sub>-O-py]} (<b>4</b>) were used to prepare d<sup>8</sup>-platinum bimetallic complexes. Precursors <b>1</b> and <b>2</b> react with AgBF<sub>4</sub> and 7-azaindole (H<i>az</i>) to give [Pt{κ<sup>3</sup>-<i>N,C,N</i>-[py-C<sub>6</sub>HMe<sub>2</sub>-py]}{κ<sup>1</sup>-<i>N</i>-[H<i>az</i>]}]BF<sub>4</sub> (<b>5</b>) and [Pt{κ<sup>3</sup>-<i>N,C,N</i>-[py-O-C<sub>6</sub>H<sub>3</sub>-O-py]}{κ<sup>1</sup>-<i>N</i>-[H<i>az</i>]}]BF<sub>4</sub> (<b>6</b>) and <b>3</b> and <b>4</b> with indolo[2,3-<i>b</i>]indole (H<sub>2</sub><i>ii</i>) to generate Pt{κ<sup>1</sup>-<i>N</i>-[H<i>ii</i>]}{κ<sup>3</sup>-<i>N,C,N</i>-[py-C<sub>6</sub>HMe<sub>2</sub>-py]} (<b>7</b>) and Pt{κ<sup>1</sup>-<i>N</i>-[H<i>ii</i>]}{κ<sup>3</sup>-<i>N,C,N</i>-[py-O-C<sub>6</sub>H<sub>3</sub>-O-py]} (<b>8</b>). Subsequent addition of <b>3</b> and <b>4</b> to <b>5</b>-<b>7</b> affords bimetallic derivatives [{Pt[κ<sup>3</sup>-<i>N,C,N</i>-(py-C<sub>6</sub>HMe<sub>2</sub>-py)]}<sub>2</sub>{μ-<i>N,N</i>-[<i>az</i>]}]BF<sub>4</sub> (<b>9</b>), [{Pt[κ<sup>3</sup>-<i>N,C,N</i>-(py-O-C<sub>6</sub>H<sub>3</sub>-O-py)]}<sub>2</sub>{μ-<i>N,N</i>-[<i>az</i>]}]BF<sub>4</sub> (<b>10</b>), and {Pt[κ<sup>3</sup>-<i>N,C,N</i>-(py-C<sub>6</sub>HMe<sub>2</sub>-py)]}<sub>2</sub>{μ-<i>N,N</i>-[<i>ii</i>]} (<b>11</b>). X-ray structures of <b>9</b>-<b>11</b> reveal separations between the metals in sequence <b>9</b> (3.0515(4) Å) < <b>10</b> (3.2689(9) Å) < <b>11</b> (3.2949(2) Å). DFT calculations support σ overlap of the dz<sup>2</sup> orbitals of platinum atoms, for <b>9</b> and <b>10</b>. Accordingly, their absorption spectra show a MMLCT transition. Complex <b>9</b> is a red emitter. The excited state has <sup>3</sup>MMLCT characteristics and a Pt-Pt separation of 2.763 Å. Complex <b>11</b> is a dual emitter in the red and NIR regions, in solid. Both excited states have a <sup>3</sup>LC/LMCT characteristic and platinum-platinum separations of 3.290 and 3.202 Å. Intermediate <b>5</b> is a green emitter that achieves quantum yields close to unity, when diluted in PMMA and 1,2-dichloroethane at low concentrations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141726562","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
Visible-Light Photocatalytic Degradation Efficiency of Tetracycline and Rhodamine B Using a Double Z-Scheme Heterojunction Catalyst of UiO-66-NH2/BiOCl/Bi2S3. 使用 UiO-66-NH2/BiOCl/Bi2S3 双 Z 型异质结催化剂的四环素和罗丹明 B 可见光光催化降解效率。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1021/acs.inorgchem.4c01917
Zijie Xia, Linlin Wang, Wenqi Tan, Linying Yuan, Xinhua He, Juan Wang, Luyang Chen, Suyuan Zeng, Shigang Lu, Zheng Jiao

BiOCl is a promising photocatalyst, but due to its weak visible light absorption capacity and low photogenerated electron-hole pair separation rate, its practical application is limited to a certain extent. In this study, a novel double Z-scheme heterojunction UiO-66-NH2/BiOCl/Bi2S3 catalyst was constructed to broaden the visible light response range and promote high photogenerated hole-electron separation of BiOCl. Its photocatalytic performance is evaluated by dissociating tetracycline (TC) and rhodamine B (RhB) in visible light. The optimal proportion of UiO-66-NH2/BiOCl/Bi2S3 hybrids exhibits the best degradation efficiency of visible light illumination (∼93% in 120 min for TC and ∼98% in 60 min for RhB). The synergistic effect of a large visible light response range and the Z-scheme charge transfer mechanism ensure the excellent visible photocatalytic activity of UiO-66-NH2/BiOCl/Bi2S3. It is proven that h+ and •O2- are the main active substances in the photocatalysis process by active substance capture experiments and electron spin resonance tests. The intermediates and degradation processes are analyzed by high-performance liquid chromatography-mass spectrometry. This study proves that the new UiO-66-NH2/BiOCl/Bi2S3 photocatalyst has great application potential in the field of water pollution degradation and will provide a new idea for the optimization of BiOCl.

BiOCl 是一种前景广阔的光催化剂,但由于其较弱的可见光吸收能力和较低的光生电子-空穴对分离率,其实际应用受到一定限制。本研究构建了一种新型双 Z 型异质结 UiO-66-NH2/BiOCl/Bi2S3 催化剂,以拓宽 BiOCl 的可见光响应范围并促进其光生化空穴电子对的高分离率。通过在可见光下解离四环素(TC)和罗丹明 B(RhB),对其光催化性能进行了评估。最佳比例的 UiO-66-NH2/BiOCl/Bi2S3 混合物在可见光照射下表现出最佳降解效率(120 分钟内对 TC 的降解效率为 93%,60 分钟内对 RhB 的降解效率为 98%)。较大的可见光响应范围和 Z 型电荷转移机制的协同效应确保了 UiO-66-NH2/BiOCl/Bi2S3 卓越的可见光光催化活性。通过活性物质捕获实验和电子自旋共振测试证明,h+和-O2-是光催化过程中的主要活性物质。高效液相色谱-质谱法对中间产物和降解过程进行了分析。该研究证明了新型 UiO-66-NH2/BiOCl/Bi2S3 光催化剂在水污染降解领域具有巨大的应用潜力,并将为 BiOCl 的优化提供新的思路。
{"title":"Visible-Light Photocatalytic Degradation Efficiency of Tetracycline and Rhodamine B Using a Double Z-Scheme Heterojunction Catalyst of UiO-66-NH<sub>2</sub>/BiOCl/Bi<sub>2</sub>S<sub>3</sub>.","authors":"Zijie Xia, Linlin Wang, Wenqi Tan, Linying Yuan, Xinhua He, Juan Wang, Luyang Chen, Suyuan Zeng, Shigang Lu, Zheng Jiao","doi":"10.1021/acs.inorgchem.4c01917","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01917","url":null,"abstract":"<p><p>BiOCl is a promising photocatalyst, but due to its weak visible light absorption capacity and low photogenerated electron-hole pair separation rate, its practical application is limited to a certain extent. In this study, a novel double Z-scheme heterojunction UiO-66-NH<sub>2</sub>/BiOCl/Bi<sub>2</sub>S<sub>3</sub> catalyst was constructed to broaden the visible light response range and promote high photogenerated hole-electron separation of BiOCl. Its photocatalytic performance is evaluated by dissociating tetracycline (TC) and rhodamine B (RhB) in visible light. The optimal proportion of UiO-66-NH<sub>2</sub>/BiOCl/Bi<sub>2</sub>S<sub>3</sub> hybrids exhibits the best degradation efficiency of visible light illumination (∼93% in 120 min for TC and ∼98% in 60 min for RhB). The synergistic effect of a large visible light response range and the Z-scheme charge transfer mechanism ensure the excellent visible photocatalytic activity of UiO-66-NH<sub>2</sub>/BiOCl/Bi<sub>2</sub>S<sub>3</sub>. It is proven that h<sup>+</sup> and •O<sub>2</sub><sup>-</sup> are the main active substances in the photocatalysis process by active substance capture experiments and electron spin resonance tests. The intermediates and degradation processes are analyzed by high-performance liquid chromatography-mass spectrometry. This study proves that the new UiO-66-NH<sub>2</sub>/BiOCl/Bi<sub>2</sub>S<sub>3</sub> photocatalyst has great application potential in the field of water pollution degradation and will provide a new idea for the optimization of BiOCl.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141726510","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
Capturing Mercury-197m/g for Auger Electron Therapy and Cancer Theranostic with Sulfur-Containing Cyclen-Based Macrocycles. 利用含硫环烯基大环捕获汞-197m/g,用于欧杰电子疗法和癌症治疗。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1021/acs.inorgchem.4c02418
Marianna Tosato, Parmissa Randhawa, Mattia Asti, Lars B S Hemmingsen, Catriona Ann O'Shea, Pravena Thaveenrasingam, Stephan P A Sauer, Shaohuang Chen, Claudia Graiff, Ileana Menegazzo, Marco Baron, Valery Radchenko, Caterina F Ramogida, Valerio Di Marco

The interest in mercury radioisotopes, 197mHg (t1/2 = 23.8 h) and 197gHg (t1/2 = 64.14 h), has recently been reignited by the dual diagnostic and therapeutic nature of their nuclear decays. These isotopes emit γ-rays suitable for single photon emission computed tomography imaging and Auger electrons which can be exploited for treating small and metastatic tumors. However, the clinical utilization of 197m/gHg radionuclides is obstructed by the lack of chelators capable of securely binding them to tumor-seeking vectors. This work aims to address this challenge by investigating a series of chemically tailored macrocyclic platforms with sulfur-containing side arms, namely, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), and 1,7-bis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane-4,10-diacetic acid (DO2A2S). 1,4,7,10-Tetrazacyclododecane-1,4,7,10-tetracetic acid (DOTA), the widest explored chelator in nuclear medicine, and the nonfunctionalized backbone 1,4,7,10-tetrazacyclododecane (cyclen) were considered as well to shed light on the role of the sulfanyl arms in the metal coordination. To this purpose, a comprehensive experimental and theoretical study encompassing aqueous coordination chemistry investigations through potentiometry, nuclear magnetic resonance (NMR) spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations, as well as concentration- and temperature-dependent [197m/gHg]Hg2+ radiolabeling and in vitro stability assays in human serum was conducted. The obtained results reveal that the investigated chelators rapidly complex Hg2+ in aqueous media, forming extremely thermodynamically stable 1:1 metal-to-ligand complexes with superior stabilities compared to those of DOTA or cyclen. These complexes exhibited 6- to 8-fold coordination environments, with donors statically bound to the metal center, as evidenced by the presence of 1H-199Hg spin-spin coupling via NMR. A similar octacoordinated environment was also found for DOTA in both solution and solid state, but in this case, multiple slowly exchanging conformers were detected at ambient temperature. The sulfur-rich ligands quantitatively incorporate cyclotron-produced [197m/gHg]Hg2+ under relatively mild reaction conditions (pH = 7 and T = 50 °C), with the resulting radioactive complexes exhibiting decent stability in human serum (up to 75% after 24 h). By developing viable chelators and understanding the impact of structural modifications, our research addresses the scarcity of suitable chelating agents for 197m/gHg, offering promise for its future in vivo application as a theranostic Auger-emitter radiometal.

197mHg(t1/2 = 23.8 小时)和 197gHg(t1/2 = 64.14 小时)这两种汞放射性同位素的核衰变具有诊断和治疗的双重性质,最近再次引起了人们的兴趣。这些同位素发射的 γ 射线适用于单光子发射计算机断层扫描成像,而奥杰电子则可用于治疗小肿瘤和转移性肿瘤。然而,由于缺乏能将 197m/gHg 放射性核素与肿瘤靶向载体安全结合的螯合剂,其临床应用受到了阻碍。这项工作旨在通过研究一系列具有含硫侧臂的化学定制大环平台,即 1,4,7,10-四[2-(甲硫基)乙基]-1,4,7,10-四氮杂环十二烷,来应对这一挑战、10-四氮杂环十二烷(DO4S)、1,4,7-三[2-(甲硫基)乙基]-1,4,7,10-四氮杂环十二烷(DO3S)和 1,7-双[2-(甲硫基)乙基]-1,4,7,10-四氮杂环十二烷-4,10-二乙酸(DO2A2S)。同时还考虑了核医学中应用最广泛的螯合剂--1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸(DOTA),以及非功能化骨架 1,4,7,10-四氮杂环十二烷(cyclen),以揭示硫酰臂在金属配位中的作用。为此,研究人员进行了全面的实验和理论研究,包括通过电位测定法、核磁共振(NMR)光谱学、X 射线晶体学和密度泛函理论(DFT)计算进行的水配位化学研究,以及浓度和温度依赖性 [197m/gHg]Hg2+ 放射性标记和人血清中的体外稳定性检测。研究结果表明,所研究的螯合剂能在水介质中快速络合 Hg2+,形成热力学上极其稳定的 1:1 金属配体复合物,其稳定性优于 DOTA 或环烯。这些配合物呈现出 6 至 8 倍配位环境,供体与金属中心静态结合,通过核磁共振发现的 1H-199Hg 自旋-自旋耦合证明了这一点。在溶液和固态中,DOTA 也发现了类似的八配位环境,但在这种情况下,在环境温度下检测到了多个缓慢交换的构象。在相对温和的反应条件下(pH = 7 和 T = 50°C),富硫配体定量掺入了回旋加速器产生的[197m/gHg]Hg2+,所产生的放射性复合物在人体血清中表现出良好的稳定性(24 小时后高达 75%)。通过开发可行的螯合剂和了解结构修饰的影响,我们的研究解决了 197m/gHg 缺乏合适螯合剂的问题,为其未来作为治疗奥杰辐射金属的体内应用提供了希望。
{"title":"Capturing Mercury-197m/g for Auger Electron Therapy and Cancer Theranostic with Sulfur-Containing Cyclen-Based Macrocycles.","authors":"Marianna Tosato, Parmissa Randhawa, Mattia Asti, Lars B S Hemmingsen, Catriona Ann O'Shea, Pravena Thaveenrasingam, Stephan P A Sauer, Shaohuang Chen, Claudia Graiff, Ileana Menegazzo, Marco Baron, Valery Radchenko, Caterina F Ramogida, Valerio Di Marco","doi":"10.1021/acs.inorgchem.4c02418","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02418","url":null,"abstract":"<p><p>The interest in mercury radioisotopes, <sup>197m</sup>Hg (<i>t</i><sub>1/2</sub> = 23.8 h) and <sup>197g</sup>Hg (<i>t</i><sub>1/2</sub> = 64.14 h), has recently been reignited by the dual diagnostic and therapeutic nature of their nuclear decays. These isotopes emit γ-rays suitable for single photon emission computed tomography imaging and Auger electrons which can be exploited for treating small and metastatic tumors. However, the clinical utilization of <sup>197m/g</sup>Hg radionuclides is obstructed by the lack of chelators capable of securely binding them to tumor-seeking vectors. This work aims to address this challenge by investigating a series of chemically tailored macrocyclic platforms with sulfur-containing side arms, namely, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), and 1,7-bis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane-4,10-diacetic acid (DO2A2S). 1,4,7,10-Tetrazacyclododecane-1,4,7,10-tetracetic acid (DOTA), the widest explored chelator in nuclear medicine, and the nonfunctionalized backbone 1,4,7,10-tetrazacyclododecane (cyclen) were considered as well to shed light on the role of the sulfanyl arms in the metal coordination. To this purpose, a comprehensive experimental and theoretical study encompassing aqueous coordination chemistry investigations through potentiometry, nuclear magnetic resonance (NMR) spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations, as well as concentration- and temperature-dependent [<sup>197m/g</sup>Hg]Hg<sup>2+</sup> radiolabeling and <i>in vitro</i> stability assays in human serum was conducted. The obtained results reveal that the investigated chelators rapidly complex Hg<sup>2+</sup> in aqueous media, forming extremely thermodynamically stable 1:1 metal-to-ligand complexes with superior stabilities compared to those of DOTA or cyclen. These complexes exhibited 6- to 8-fold coordination environments, with donors statically bound to the metal center, as evidenced by the presence of <sup>1</sup>H-<sup>199</sup>Hg spin-spin coupling <i>via</i> NMR. A similar octacoordinated environment was also found for DOTA in both solution and solid state, but in this case, multiple slowly exchanging conformers were detected at ambient temperature. The sulfur-rich ligands quantitatively incorporate cyclotron-produced [<sup>197m/g</sup>Hg]Hg<sup>2+</sup> under relatively mild reaction conditions (pH = 7 and <i>T</i> = 50 °C), with the resulting radioactive complexes exhibiting decent stability in human serum (up to 75% after 24 h). By developing viable chelators and understanding the impact of structural modifications, our research addresses the scarcity of suitable chelating agents for <sup>197m/g</sup>Hg, offering promise for its future <i>in vivo</i> application as a theranostic Auger-emitter radiometal.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141722663","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, Physical, and Magnetocaloric Properties of MgZn2-Type Gd2Al3Rh. MgZn2 型 Gd2Al3Rh 的合成、物理和磁性。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1021/acs.inorgchem.4c01887
Fabian Eustermann, Frank Stegemann, Oliver Janka

Gd2Al3Rh was synthesized from the elements using arc-melting techniques, along with subsequent annealing. The title compound adopts the hexagonal MgZn2 type structure (space group P63/mmc, hP12, Wyckoff sequence hfa) with the Gd atoms found on the Mg positions (4f), the Rh (2a) and Al (6h) atoms occupying the two Zn sites of the prototype. In addition, mixing of Rh and Al on both crystallographic positions is observed. The magnetic susceptibility and magnetization experiments were conducted indicating ferromagnetic ordering below the Curie temperature of TC = 51.3(1) K and very high magnetization of 6.96(1) μB at 3 K and 70 kOe. In addition, heat capacity and electrical resistivity measurements were conducted. The magnetocaloric properties of ferromagnetic Gd2Al3Rh have been determined by means of magnetization measurements. For a field change of ΔH = 0 → 50 kOe the magnetic entropy change equals ΔSMmax = -4.8 J kg-1 K-1, leading to a relative cooling power of RCP = 283 J kg-1 for the same field change. The adiabatic temperature change was estimated to be ΔTadmax = 2.1 K using the heat capacity data.

Gd2Al3Rh 是利用电弧熔融技术从元素中合成的,随后进行了退火处理。标题化合物采用六方 MgZn2 型结构(空间群 P63/mmc,hP12,Wyckoff 序列 hfa),钆原子位于镁原子位置(4f),Rh 原子(2a)和 Al 原子(6h)占据原型的两个 Zn 位点。此外,在两个晶体学位置上还观察到 Rh 原子和 Al 原子的混合。磁感应强度和磁化率实验表明,铁磁有序性低于居里温度 TC = 51.3(1) K,在 3 K 和 70 kOe 时磁化率高达 6.96(1) μB。此外,还进行了热容量和电阻率测量。通过磁化测量确定了铁磁性 Gd2Al3Rh 的磁ocaloric 特性。当磁场变化为 ΔH = 0 → 50 kOe 时,磁熵变化等于 ΔSMmax = -4.8 J kg-1 K-1,因此在相同的磁场变化下,相对冷却功率为 RCP = 283 J kg-1。根据热容量数据,绝热温度变化估计为 ΔTadmax = 2.1 K。
{"title":"Synthesis, Physical, and Magnetocaloric Properties of MgZn<sub>2</sub>-Type Gd<sub>2</sub>Al<sub>3</sub>Rh.","authors":"Fabian Eustermann, Frank Stegemann, Oliver Janka","doi":"10.1021/acs.inorgchem.4c01887","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01887","url":null,"abstract":"<p><p>Gd<sub>2</sub>Al<sub>3</sub>Rh was synthesized from the elements using arc-melting techniques, along with subsequent annealing. The title compound adopts the hexagonal MgZn<sub>2</sub> type structure (space group <i>P</i>6<sub>3</sub>/<i>mmc</i>, <i>hP</i>12, Wyckoff sequence <i>hfa</i>) with the Gd atoms found on the Mg positions (4<i>f</i>), the Rh (2<i>a</i>) and Al (6<i>h</i>) atoms occupying the two Zn sites of the prototype. In addition, mixing of Rh and Al on both crystallographic positions is observed. The magnetic susceptibility and magnetization experiments were conducted indicating ferromagnetic ordering below the Curie temperature of <i>T</i><sub>C</sub> = 51.3(1) K and very high magnetization of 6.96(1) μ<sub>B</sub> at 3 K and 70 kOe. In addition, heat capacity and electrical resistivity measurements were conducted. The magnetocaloric properties of ferromagnetic Gd<sub>2</sub>Al<sub>3</sub>Rh have been determined by means of magnetization measurements. For a field change of Δ<i>H</i> = 0 → 50 kOe the magnetic entropy change equals Δ<i>S</i><sub>M</sub><sup>max</sup> = -4.8 J kg<sup>-1</sup> K<sup>-1</sup>, leading to a relative cooling power of RCP = 283 J kg<sup>-1</sup> for the same field change. The adiabatic temperature change was estimated to be Δ<i>T</i><sub>ad</sub><sup>max</sup> = 2.1 K using the heat capacity data.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141631942","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
Rhodium(I) Complexes with a η1-Fluorenyl-P-phosphanylphosphorane Ligand. 带有 η1-Fluorenyl-P-phosphanylphosphorane 配体的铑(I)配合物。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1021/acs.inorgchem.4c01934
Javier Eusamio, Nil Saumell, Anton Vidal-Ferran, Arnald Grabulosa

The first example of a P-phosphanylphosphorane, Flu═PCy2-PCy2 (L2; Flu = 9-fluorenyl), has been easily prepared by P-phosphination of lithiated 9-dicyclohexylphosphinofluorene (FluPCy2, L0) with chlorodicyclohexylphosphane. L2 constitutes a new type of P(III)-P(V) organophosphorus compound, a σ3λ34λ5 species that is stable under an inert atmosphere in the solid state. The reaction of L2 with [Rh(diene)2]BR4 causes metalation of the benzylic carbon (C9) of fluorene, giving κ2-C,P complexes in which fluorene is coordinated in the η1 form. A complex with the weakly coordinating BArF anion has been isolated and fully characterized, including its crystal structure obtained by X-ray diffraction.

通过将石碳酸化的 9-二环己基膦芴(FluPCy2,L0)与氯二环己基膦烷进行 P-膦化反应,可轻松制备出第一个 P-膦基膦烷--Flu═PCy2-PCy2(L2;Flu = 9-芴基)。L2 是一种新型 P(III)-P(V)有机磷化合物,属于 σ3λ3-σ4λ5 物种,在固态惰性气氛下非常稳定。L2 与 [Rh(diene)2]BR4 反应会导致芴的苄基碳(C9)金属化,从而产生κ2-C,P 复合物,其中芴以 η1 形式配位。我们已分离出一种与弱配位 BArF 阴离子的配合物,并对其进行了全面鉴定,包括通过 X 射线衍射获得其晶体结构。
{"title":"Rhodium(I) Complexes with a η<sup>1</sup>-Fluorenyl-<i>P</i>-phosphanylphosphorane Ligand.","authors":"Javier Eusamio, Nil Saumell, Anton Vidal-Ferran, Arnald Grabulosa","doi":"10.1021/acs.inorgchem.4c01934","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01934","url":null,"abstract":"<p><p>The first example of a <i>P</i>-phosphanylphosphorane, Flu═PCy<sub>2</sub>-PCy<sub>2</sub> (<b>L2</b>; Flu = 9-fluorenyl), has been easily prepared by P-phosphination of lithiated 9-dicyclohexylphosphinofluorene (FluPCy<sub>2</sub>, <b>L0</b>) with chlorodicyclohexylphosphane. <b>L2</b> constitutes a new type of P(III)-P(V) organophosphorus compound, a σ<sup>3</sup>λ<sup>3</sup>-σ<sup>4</sup>λ<sup>5</sup> species that is stable under an inert atmosphere in the solid state. The reaction of <b>L2</b> with [Rh(diene)<sub>2</sub>]BR<sub>4</sub> causes metalation of the benzylic carbon (C9) of fluorene, giving κ<sup>2</sup>-C,P complexes in which fluorene is coordinated in the η<sup>1</sup> form. A complex with the weakly coordinating BArF anion has been isolated and fully characterized, including its crystal structure obtained by X-ray diffraction.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141631939","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
Picosecond Metal-to-Ligand Charge-Transfer Deactivation in Co(ppy)3 via Jahn-Teller Distortion. 通过 Jahn-Teller 扭曲实现 Co(ppy)3 中的皮秒金属-配体电荷转移失活。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1021/acs.inorgchem.4c01959
Justin T Malme, Jenelle N Weaver, Gregory S Girolami, Josh Vura-Weis

The excited-state dynamics of fac-Co(ppy)3, where ppy = 2-[2-(pyridyl)phenyl], are measured with femtosecond UV-vis transient absorption spectroscopy. The initial state is confirmed with spectroelectrochemistry to have significant metal-to-ligand charge transfer (MLCT) character, unlike other Co complexes that generally have ligand-to-metal charge transfer or ligand-field transitions in this energy range. Ground-state recovery occurs in 8.65 ps in dichloromethane. Density functional theory calculations show that the MLCT state undergoes Jahn-Teller distortion and converts to a five-coordinate triplet metal-centered state in which one Co-N bond is broken. The results highlight a potential pitfall of heteroleptic bidentate ligands when designing strong-field ligands for transition-metal chromophores.

飞秒紫外-可见瞬态吸收光谱测量了 fac-Co(PYY)3(其中 ppy = 2-[2-(吡啶基)苯基])的激发态动力学。通过光谱电化学方法证实,初始态具有显著的金属-配体电荷转移(MLCT)特性,这与其他钴配合物不同,其他钴配合物在这一能量范围内通常具有配体-金属电荷转移或配体-场转变。在二氯甲烷中,基态恢复时间为 8.65 ps。密度泛函理论计算表明,MLCT 状态发生了 Jahn-Teller 畸变,并转化为五配位三重金属中心态,其中一个 Co-N 键断裂。研究结果突显了在为过渡金属发色团设计强场配体时,异性双齿配体的潜在隐患。
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引用次数: 0
Supramolecular Binding of Phosphonate Dianions by Nanojars and Nanojar Clamshells. 纳米琼脂和纳米琼脂蛤壳对膦酸盐滇离子的超分子结合。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1021/acs.inorgchem.4c02386
Pooja Singh, Matthias Zeller, Gellert Mezei

Despite the widespread use of phosphonates (RPO32-) in various agricultural, industrial, and household applications and the ensuing eutrophication of polluted water bodies, the capture of phosphonate ions by molecular receptors has been scarcely studied. Herein, we describe a novel approach to phosphonate binding using chemically and thermally robust supramolecular coordination assemblies of the formula [RPO3⊂{cis-CuII(μ-OH)(μ-pz)}n]2- (Cun; n = 27-31; pz = pyrazolate ion, C3H3N2-; R = aliphatic or aromatic group). The neutral receptors, termed nanojars, strongly bind phosphonate anions by a multitude of hydrogen bonds within their highly hydrophilic cavities. These nanojars can be synthesized either directly from their constituents or by depolymerization of [trans-CuII(μ-OH)(μ-pz)] induced by phosphonate anions. Electrospray-ionization mass spectrometry, UV-vis and variable-temperature, paramagnetic 1H and 31P NMR spectroscopy, single-crystal X-ray diffraction, along with chemical stability studies toward NH3 and Ba2+ ions, and thermal stability studies in solution are employed to explore the binding of various phosphonate ions by nanojars. Crystallographic studies of 12 different nanojars offer unprecedented structural characterization of host-guest complexes with doubly charged RPO32- ions and reveal a new motif in nanojar chemistry, nanojar clamshells, which consist of phosphonate anion-bridged pairs of nanojars and double the phosphonate-binding capacity of nanojars.

尽管膦酸盐(RPO32-)在各种农业、工业和家庭应用中被广泛使用,并随之导致污染水体富营养化,但分子受体捕获膦酸盐离子的研究却很少。在此,我们介绍了一种利用化学和热稳定性超分子配位组装体[RPO3⊂{cis-CuII(μ-OH)(μ-pz)}n]2-(Cun;n = 27-31;pz = 吡唑烷离子,C3H3N2-;R = 脂肪族或芳香族基团)结合膦酸盐的新方法。这种中性受体被称为纳米琼脂,在其高度亲水的空腔中通过大量氢键与膦酸阴离子紧密结合。这些纳米琼脂可以直接从其成分中合成,也可以在膦酸阴离子的诱导下通过[反式-CuII(μ-OH)(μ-pz)]∞的解聚作用合成。利用电喷雾离子化质谱法、紫外-可见光光谱法、变温顺磁 1H 和 31P NMR 光谱法、单晶 X 射线衍射法、对 NH3 和 Ba2+ 离子的化学稳定性研究以及溶液热稳定性研究来探讨各种膦酸根离子与纳米琼脂的结合。对 12 种不同纳米琼脂的晶体学研究提供了前所未有的带双电荷 RPO32- 离子的主客复合物的结构特征,并揭示了纳米琼脂化学中的一种新模式--纳米琼脂蛤壳,它由膦酸盐阴离子桥对纳米琼脂组成,并使纳米琼脂的膦酸盐结合能力加倍。
{"title":"Supramolecular Binding of Phosphonate Dianions by Nanojars and Nanojar Clamshells.","authors":"Pooja Singh, Matthias Zeller, Gellert Mezei","doi":"10.1021/acs.inorgchem.4c02386","DOIUrl":"10.1021/acs.inorgchem.4c02386","url":null,"abstract":"<p><p>Despite the widespread use of phosphonates (RPO<sub>3</sub><sup>2-</sup>) in various agricultural, industrial, and household applications and the ensuing eutrophication of polluted water bodies, the capture of phosphonate ions by molecular receptors has been scarcely studied. Herein, we describe a novel approach to phosphonate binding using chemically and thermally robust supramolecular coordination assemblies of the formula [RPO<sub>3</sub>⊂{<i>cis</i>-Cu<sup>II</sup>(μ-OH)(μ-pz)}<sub><i>n</i></sub>]<sup>2-</sup> (Cu<sub><i>n</i></sub>; <i>n</i> = 27-31; pz = pyrazolate ion, C<sub>3</sub>H<sub>3</sub>N<sub>2</sub><sup>-</sup>; R = aliphatic or aromatic group). The neutral receptors, termed nanojars, strongly bind phosphonate anions by a multitude of hydrogen bonds within their highly hydrophilic cavities. These nanojars can be synthesized either directly from their constituents or by depolymerization of [<i>trans</i>-Cu<sup>II</sup>(μ-OH)(μ-pz)]<sub>∞</sub> induced by phosphonate anions. Electrospray-ionization mass spectrometry, UV-vis and variable-temperature, paramagnetic <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy, single-crystal X-ray diffraction, along with chemical stability studies toward NH<sub>3</sub> and Ba<sup>2+</sup> ions, and thermal stability studies in solution are employed to explore the binding of various phosphonate ions by nanojars. Crystallographic studies of 12 different nanojars offer unprecedented structural characterization of host-guest complexes with doubly charged RPO<sub>3</sub><sup>2-</sup> ions and reveal a new motif in nanojar chemistry, nanojar clamshells, which consist of phosphonate anion-bridged pairs of nanojars and double the phosphonate-binding capacity of nanojars.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141631941","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
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Inorganic Chemistry
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