Xing Wang, Gbemi Abass, Jiajia Wang, Dan Song, Aibin Ma
Density functional theory calculations have been performed to compare the HCHO decomposition on Co3O4 (110)-A and (110)-B terminations. The results showed that the energy barriers of two C-H bond cleavage of HCHO on (110)-A termination were both lower than that on (110)-B termination, suggesting that the (110)-A termination had stronger HCHO decomposition ability than the (110)-B termination. Electronic structures revealed that the stronger HCHO decomposition ability of (110)-A termination might be ascribed to the strong covalent bond between HCHO and (110)-A termination, as well as the higher d-band center of Co3+ ion on (110)-A termination. Furthermore, we proposed that the preparation of Co3O4 under the oxygen-rich growth condition was beneficial to HCHO decomposition because the (110)-A termination was more stable under the oxygen-rich condition.
{"title":"A comparative DFT study of HCHO decomposition on different terminations of the Co3O4 (110) surface","authors":"Xing Wang, Gbemi Abass, Jiajia Wang, Dan Song, Aibin Ma","doi":"10.1039/d4dt01068j","DOIUrl":"https://doi.org/10.1039/d4dt01068j","url":null,"abstract":"Density functional theory calculations have been performed to compare the HCHO decomposition on Co3O4 (110)-A and (110)-B terminations. The results showed that the energy barriers of two C-H bond cleavage of HCHO on (110)-A termination were both lower than that on (110)-B termination, suggesting that the (110)-A termination had stronger HCHO decomposition ability than the (110)-B termination. Electronic structures revealed that the stronger HCHO decomposition ability of (110)-A termination might be ascribed to the strong covalent bond between HCHO and (110)-A termination, as well as the higher d-band center of Co3+ ion on (110)-A termination. Furthermore, we proposed that the preparation of Co3O4 under the oxygen-rich growth condition was beneficial to HCHO decomposition because the (110)-A termination was more stable under the oxygen-rich condition.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495837","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}
Luyao Chen, Wei Hu, Chuan Xiao, Caijin Lei, Teng Zhu, Chengchuang Li, Jie Tang, Guangbin Cheng, Hongwei Yang
In recent years, with the development of deep coal mines and petroleum resources and the expansion of the aerospace industry, the pursuit of heat-resistant energetic materials with high thermal stability and high energy has been increasing. Bis(4-nitropyrazole) was employed as an energy bridge to link 1,2,4-triazole, thereby constructing a sophisticated tetracyclic framework in this study. A tetracyclic heat-resistant explosive 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) (3) and its derivative 6 - 8 with excellent comprehensive performance have been successfully prepared. Particularly noteworthy is that compound 3 has a detonation velocity of 8604 m/s, which exceeds that of the conventional heat-resistant explosive HNS with a velocity of 7164 m/s. Furthermore, compound 3 has higher thermal stability (Td = 340 °C) than HNS (Td = 318 °C). In addition, tetracyclic compound 3 also exhibited extraordinarily low sensitivity (IS > 40 J; FS > 360 N). These unique characteristics make it a potential candidate for novel heat-resistant and insensitive energetic materials.
{"title":"Advanced Tetracyclic Heat-resistant Energetic Materials Based on Bis (4-nitropyrazole) Bridged 1,2,4-triazole","authors":"Luyao Chen, Wei Hu, Chuan Xiao, Caijin Lei, Teng Zhu, Chengchuang Li, Jie Tang, Guangbin Cheng, Hongwei Yang","doi":"10.1039/d4dt01627k","DOIUrl":"https://doi.org/10.1039/d4dt01627k","url":null,"abstract":"In recent years, with the development of deep coal mines and petroleum resources and the expansion of the aerospace industry, the pursuit of heat-resistant energetic materials with high thermal stability and high energy has been increasing. Bis(4-nitropyrazole) was employed as an energy bridge to link 1,2,4-triazole, thereby constructing a sophisticated tetracyclic framework in this study. A tetracyclic heat-resistant explosive 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) (3) and its derivative 6 - 8 with excellent comprehensive performance have been successfully prepared. Particularly noteworthy is that compound 3 has a detonation velocity of 8604 m/s, which exceeds that of the conventional heat-resistant explosive HNS with a velocity of 7164 m/s. Furthermore, compound 3 has higher thermal stability (Td = 340 °C) than HNS (Td = 318 °C). In addition, tetracyclic compound 3 also exhibited extraordinarily low sensitivity (IS > 40 J; FS > 360 N). These unique characteristics make it a potential candidate for novel heat-resistant and insensitive energetic materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495507","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}
Liangliang Huang, Tao Peng, Yansheng Gong, Rui Wang, Beibei He, Jun Jin, Huanwen Wang
Photocatalytic ammonia production holds immense promise as an environmentally sustainable approach to nitrogen fixation. In this study, In2O3/In2S3-ZnCdS ternary heterostructures were successfully constructed through an innovative in-situ anion exchange process, coupled with a low-temperature hydrothermal method for ZnCdS (ZCS) incorporation. The resulting In2O3/In2S3-ZCS photocatalyst was proved to be highly efficient in converting N2 to NH3 under mild conditions, eliminating the need for sacrificial agents or precious metal catalysts. Notably, the NH4+ yield of In2O3/In2S3-0.5ZCS reached a significant level of 71.2 μmol·g-1·h-1, which was 10.47 times higher than that of In2O3 (6.8 μmol·g-1·h-1) and 3.22 times higher than that of In2O3/In2S3 (22.1 μmol·g-1·h-1). This outstanding performance can be attributed to the ternary heterojunction configuration, which significantly extends the lifetime of photogenerated carriers and enhances the spatial separation of electrons and holes. The synergistic interplay between CdZnS, In₂S₃, and In₂O₃ in the heterojunction facilitates electron transport, thereby boosting the rate of the photocatalytic nitrogen fixation reaction. Our study not only validates the efficacy of ternary heterojunctions in photocatalytic nitrogen fixation but also offers valuable insights for the design and construction of such catalysts for future applications.
{"title":"Construction of hierarchical In2O3/In2S3-ZnCdS ternary microsphere heterostructures for efficient photocatalytic nitrogen fixation","authors":"Liangliang Huang, Tao Peng, Yansheng Gong, Rui Wang, Beibei He, Jun Jin, Huanwen Wang","doi":"10.1039/d4dt01605j","DOIUrl":"https://doi.org/10.1039/d4dt01605j","url":null,"abstract":"Photocatalytic ammonia production holds immense promise as an environmentally sustainable approach to nitrogen fixation. In this study, In2O3/In2S3-ZnCdS ternary heterostructures were successfully constructed through an innovative in-situ anion exchange process, coupled with a low-temperature hydrothermal method for ZnCdS (ZCS) incorporation. The resulting In2O3/In2S3-ZCS photocatalyst was proved to be highly efficient in converting N2 to NH3 under mild conditions, eliminating the need for sacrificial agents or precious metal catalysts. Notably, the NH4+ yield of In2O3/In2S3-0.5ZCS reached a significant level of 71.2 μmol·g-1·h-1, which was 10.47 times higher than that of In2O3 (6.8 μmol·g-1·h-1) and 3.22 times higher than that of In2O3/In2S3 (22.1 μmol·g-1·h-1). This outstanding performance can be attributed to the ternary heterojunction configuration, which significantly extends the lifetime of photogenerated carriers and enhances the spatial separation of electrons and holes. The synergistic interplay between CdZnS, In₂S₃, and In₂O₃ in the heterojunction facilitates electron transport, thereby boosting the rate of the photocatalytic nitrogen fixation reaction. Our study not only validates the efficacy of ternary heterojunctions in photocatalytic nitrogen fixation but also offers valuable insights for the design and construction of such catalysts for future applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495776","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}
Venkata Sai Sashankh Penki, Yu Ting Chu, Hsing-Yin Chen, Sri Sudewi, Chien-Hung Li, Genin Gary Huang, Sodio C. N. Hsu
A series of β-thioketiminate copper(I) complex trimers [LCuI]3 were synthesized by modifying the ligand framework with electron-withdrawing groups (F and Cl) or electron-donating groups (iPr and Me) at the N-aryl ring as well as with CF3 groups on the chelating backbone. This ligand modification significantly impacts on the enhancement of Cu···Cu short contacts, which can be rationalized by using steric and electronic factors of the chelated ligand. We observed that this intramolecular cuprophilicity among [LCuI]3 complexes is primarily governed by the size of N-aryl ortho-substituents. These findings were well supported by X-ray crystallography, Raman spectroscopy, and Mayer bond order analysis. The electronic effects induced by the ligand modification on the LCuI fragment were investigated using CO and 2,4,6-CNC6H2Me3 as probe molecules. Corroborated by the FTIR and CV measurements, our results reveal that the β-thioketiminate SN chelators induce more pronounced changes in the electronic character of LCuI fragment due to the presence of CF3 groups on the chelating backbone in comparison to the F or Cl substituents on the N-aryl ring.
通过在配体框架的 N-芳基环上加入抽电子基团（F 和 Cl）或供电子基团（iPr 和 Me）以及在螯合骨架上加入 CF3 基团，合成了一系列 β-硫酮亚胺铜(I)络合物三聚体 [LCuI]3。这种配体修饰对铜-铜短接触的增强有显著影响，这可以通过螯合配体的立体和电子因素加以合理解释。我们观察到，[LCuI]3 复合物的分子内亲杯性主要受 N-芳基正取代基大小的影响。这些发现得到了 X 射线晶体学、拉曼光谱和梅耶键序分析的有力支持。以 CO 和 2,4,6-CNC6H2Me3 为探针分子，研究了配体修饰对 LCuI 片段的电子效应。傅立叶变换红外光谱和 CV 测量结果表明，与 N 芳基环上的 F 或 Cl 取代基相比，由于螯合骨架上 CF3 基团的存在，β-硫酮亚胺 SN 螯合剂诱导 LCuI 片段的电子特性发生了更明显的变化。
{"title":"Steric and Electronic Influences on Cu-Cu Short Contacts in β-Thioketiminato Tricopper(I) Clusters","authors":"Venkata Sai Sashankh Penki, Yu Ting Chu, Hsing-Yin Chen, Sri Sudewi, Chien-Hung Li, Genin Gary Huang, Sodio C. N. Hsu","doi":"10.1039/d4dt01549e","DOIUrl":"https://doi.org/10.1039/d4dt01549e","url":null,"abstract":"A series of β-thioketiminate copper(I) complex trimers [LCu<small><sup>I</sup></small>]<small><sub>3</sub></small> were synthesized by modifying the ligand framework with electron-withdrawing groups (F and Cl) or electron-donating groups (iPr and Me) at the <em>N</em>-aryl ring as well as with CF<small><sub>3</sub></small> groups on the chelating backbone. This ligand modification significantly impacts on the enhancement of Cu···Cu short contacts, which can be rationalized by using steric and electronic factors of the chelated ligand. We observed that this intramolecular cuprophilicity among [LCu<small><sup>I</sup></small>]<small><sub>3</sub></small> complexes is primarily governed by the size of <em>N</em>-aryl ortho-substituents. These findings were well supported by X-ray crystallography, Raman spectroscopy, and Mayer bond order analysis. The electronic effects induced by the ligand modification on the LCuI fragment were investigated using CO and 2,4,6-CNC<small><sub>6</sub></small>H<small><sub>2</sub></small>Me<small><sub>3</sub></small> as probe molecules. Corroborated by the FTIR and CV measurements, our results reveal that the β-thioketiminate SN chelators induce more pronounced changes in the electronic character of LCu<small><sup>I</sup></small> fragment due to the presence of CF<small><sub>3</sub></small> groups on the chelating backbone in comparison to the F or Cl substituents on the <em>N</em>-aryl ring.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495509","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}
We designed a tris-catecholate-based siderophore mimic, H6-T-CATL, to selectively chelate iron(III) from mitochondrial cytochromes and other iron-containing proteins within cellular matrices. This strategic sequestration aims to trigger apoptosis or ferroptosis in cancer cells through the glutathione (GSH)-dependent release of reduced iron and subsequent ROS-mediated cytotoxicity. Synthesis of H6-T-CATL involved precise peptide coupling reactions. Using the Fe(III)-porphyrin model (Fe-TPP-Cl), akin to cytochrome c, we studied H6-T-CATL's ability to extract iron(III), yielding a binding constant (Krel) of 1014 for the resulting iron(III) complex (FeIII-T-CATL)₃⁻. This complex readily underwent GSH-mediated reduction to release bioavailable iron(II), which catalyzed Fenton-like reactions generating hydroxyl radicals (●OH), confirmed by spectroscopic analyses. Our research underscores the potential of H6-T-CATL to induce cancer cell death by depleting iron(III) from cellular metalloproteins, releasing pro-apoptotic iron(II). Evaluation across various cancer types, including normal cells, demonstrated H6-T-CATL's cytotoxicity through ROS production, mitochondrial dysfunction, and activation of ferroptosis and DNA damage pathways. These findings propose a novel mechanism for cancer therapy, leveraging endogenous iron stores within cells. H6-T-CATL emerges as a promising next-generation anticancer agent, exploiting iron metabolism vulnerabilities to induce selective cancer cell death through ferroptosis induction.
我们设计了一种基于三儿茶酚的嗜苷酸盐模拟物 H6-T-CATL，用于选择性地从线粒体细胞色素和细胞基质中的其他含铁蛋白质中螯合铁（III）。这种策略性螯合旨在通过谷胱甘肽（GSH）依赖性还原铁释放和随后的 ROS 介导的细胞毒性，触发癌细胞凋亡或铁凋亡。H6-T-CATL 的合成涉及精确的肽偶联反应。利用类似于细胞色素 c 的铁（III）-卟啉模型（Fe-TPP-Cl），我们研究了 H6-T-CATL 提取铁（III）的能力，结果发现铁（III）复合物（FeIII-T-CATL）₃- 的结合常数（Krel）为 1014。这种复合物很容易发生由 GSH 介导的还原反应，释放出生物可利用的铁（II），从而催化类似芬顿的反应，产生羟基自由基（●OH），光谱分析证实了这一点。我们的研究强调了 H6-T-CATL 通过消耗细胞金属蛋白中的铁(III)，释放出促进凋亡的铁(II)，从而诱导癌细胞死亡的潜力。对各种癌症类型（包括正常细胞）的评估表明，H6-T-CATL 的细胞毒性是通过产生 ROS、线粒体功能障碍以及激活铁变态反应和 DNA 损伤途径产生的。这些发现为利用细胞内的内源性铁储存治疗癌症提出了一种新的机制。H6-T-CATL 利用铁代谢的弱点，通过诱导铁氧化诱导选择性癌细胞死亡，是一种很有前途的下一代抗癌剂。
{"title":"Strategic design and development of a siderophore mimic: Pioneering anticancer therapy via ROS generation and ferroptosis","authors":"Abhishek Panwar, Anushree Lye, Dulal Musib, Aarti Upadhyay, Irungbam Karankumar, Paonam Bebika Devi, Maynak Pal, Biswanath Maity, Mithun Roy","doi":"10.1039/d4dt01461h","DOIUrl":"https://doi.org/10.1039/d4dt01461h","url":null,"abstract":"We designed a tris-catecholate-based siderophore mimic, H6-T-CATL, to selectively chelate iron(III) from mitochondrial cytochromes and other iron-containing proteins within cellular matrices. This strategic sequestration aims to trigger apoptosis or ferroptosis in cancer cells through the glutathione (GSH)-dependent release of reduced iron and subsequent ROS-mediated cytotoxicity. Synthesis of H6-T-CATL involved precise peptide coupling reactions. Using the Fe(III)-porphyrin model (Fe-TPP-Cl), akin to cytochrome c, we studied H6-T-CATL's ability to extract iron(III), yielding a binding constant (Krel) of 1014 for the resulting iron(III) complex (FeIII-T-CATL)₃⁻. This complex readily underwent GSH-mediated reduction to release bioavailable iron(II), which catalyzed Fenton-like reactions generating hydroxyl radicals (●OH), confirmed by spectroscopic analyses. Our research underscores the potential of H6-T-CATL to induce cancer cell death by depleting iron(III) from cellular metalloproteins, releasing pro-apoptotic iron(II). Evaluation across various cancer types, including normal cells, demonstrated H6-T-CATL's cytotoxicity through ROS production, mitochondrial dysfunction, and activation of ferroptosis and DNA damage pathways. These findings propose a novel mechanism for cancer therapy, leveraging endogenous iron stores within cells. H6-T-CATL emerges as a promising next-generation anticancer agent, exploiting iron metabolism vulnerabilities to induce selective cancer cell death through ferroptosis induction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495511","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}
wenjia Qu, Pengpeng Wei, Jingfang Li, Liye Liang, Li Qiang Ma, Guangming Li
Since the emission standard of global sulfur is escalated, to development of high-efficiency deep desulfurization techniques become imperative. Herein, to design a high-activity heterogeneous catalyst for aerobic oxidation desulfurization (AODS) of fuel, Dawson-type polyoxometalate (H6P2W18O62 abbreviated as D-P2W18), characterized by its high activity and strong oxidative capacity, was applied to react with CuCl2·2H2O and H3TZI by one-pot hydrothermal method. As a result, blue crystalline H6P2W18O62@[Cu6O(TZI)3(H2O)6]4 (abbreviated as D-P2W18@rht-MOF-1; rht-MOF-1 = [Cu6O(TZI)3(H2O)6]4·nH2O) was afforded. X-ray diffraction analysis indicated that D-P2W18 was successfully encapsulated in the two different cages of rht-MOF-1 which is distinct with the crystal structure of Keggin-type POMs@rht-MOF-1. It represents the first crystal structure of Dawson-type POMs@rht-MOF-1. When D-P2W18@rht-MOF-1 was employed as catalyst for AODS under ambient oxygen pressure with assistance of surfactant dioctadecyl dimethyl ammonium chloride (DODMAC), it demonstrated remarkable catalytic capability and recyclability for both model fuel and commercial diesel. Further, the AODS reaction mechanism, identified as a free radical oxidation-reduction process, was verified by way of radical quenching experiments, EPR and XPS analysis. This approach offers a feasible route for synthesis of new Dawson-type POMs@MOFs of heterogeneous catalysts for highly active AODS of fuel.
{"title":"Self-assembly of Dawson-type H6P2W18O62@[Cu6O(TZI)3(H2O)6]4 towards high performance of aerobic oxidation desulfurization of fuel","authors":"wenjia Qu, Pengpeng Wei, Jingfang Li, Liye Liang, Li Qiang Ma, Guangming Li","doi":"10.1039/d4dt01568a","DOIUrl":"https://doi.org/10.1039/d4dt01568a","url":null,"abstract":"Since the emission standard of global sulfur is escalated, to development of high-efficiency deep desulfurization techniques become imperative. Herein, to design a high-activity heterogeneous catalyst for aerobic oxidation desulfurization (AODS) of fuel, Dawson-type polyoxometalate (H6P2W18O62 abbreviated as D-P2W18), characterized by its high activity and strong oxidative capacity, was applied to react with CuCl2·2H2O and H3TZI by one-pot hydrothermal method. As a result, blue crystalline H6P2W18O62@[Cu6O(TZI)3(H2O)6]4 (abbreviated as D-P2W18@rht-MOF-1; rht-MOF-1 = [Cu6O(TZI)3(H2O)6]4·nH2O) was afforded. X-ray diffraction analysis indicated that D-P2W18 was successfully encapsulated in the two different cages of rht-MOF-1 which is distinct with the crystal structure of Keggin-type POMs@rht-MOF-1. It represents the first crystal structure of Dawson-type POMs@rht-MOF-1. When D-P2W18@rht-MOF-1 was employed as catalyst for AODS under ambient oxygen pressure with assistance of surfactant dioctadecyl dimethyl ammonium chloride (DODMAC), it demonstrated remarkable catalytic capability and recyclability for both model fuel and commercial diesel. Further, the AODS reaction mechanism, identified as a free radical oxidation-reduction process, was verified by way of radical quenching experiments, EPR and XPS analysis. This approach offers a feasible route for synthesis of new Dawson-type POMs@MOFs of heterogeneous catalysts for highly active AODS of fuel.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495767","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}
The σ-arsolido complex [Mo(AsC4Me4)(CO)3(η5-C5H5)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf) while iodomethane affords a mixture of [Me2AsC4Me4]I, [MoMe(CO)3(η5-C5H5)], [MoI(CO)3(η5-C5H5)] and the arsole complexes cisoid- and transoid-[MoI(MeAsC4Me4)(CO)2(η5-C5H5)] and transoid-[Mo{C(O)Me}(MeAsC4Me4)(CO)2(η5-C5H5)], The arsole ligand in [Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf) is readily liberated by NaI in acetone to afford free MeAsC4Me4 and [MoI(CO)3(η5-C5H5)]. In a similar manner, the reaction of [Mo(AsC4Ph4)(CO)3(η5-C5H5)] with MeI affords MeAsC4Ph4 and [MoI(CO)3(η5-C5H5)], while [Mo{AsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)] with MeOTf affords [Mo{MeAsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)](OTf). The reaction of [Mo(AsC4Me4)(CO)3(η5-C5H5)] with activated alkynes (RCCR: R = CF3, CO2Me) does not proceed via [4 + 2] cyclo-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C4Me4)CRCRCO}(CO)2(η5-C5H5)].
σ-胂络合物[Mo(AsC4Me4)(CO)3(η5-C5H5)]被 MeOTf 在砷处烷基化，得到五甲基胂络合物[Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)，而碘甲烷得到[Me2AsC4Me4]I、[MoMe(CO)3(η5-C5H5)]的混合物、[MoI(CO)3(η5-C5H5)]以及顺式和反式[MoI(MeAsC4Me4)(CO)2(η5-C5H5)]和反式[Mo{C(O)Me}(MeAsC4Me4)(CO)2(η5-C5H5)]的芳基络合物、Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)中的芳基配体很容易被丙酮中的 NaI 解离，从而得到游离的 MeAsC4Me4 和 [MoI(CO)3(η5-C5H5)]。类似地，[Mo(AsC4Ph4)(CO)3(η5-C5H5)] 与 MeI 反应生成 MeAsC4Ph4 和 [MoI(CO)3(η5-C5H5)]、而[Mo{AsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)]与 MeOTf 反应生成[Mo{MeAsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)](OTf)。Mo(AsC4Me4)(CO)3(η5-C5H5)]与活化炔（RCCR：R = CF3，CO2Me）的反应不是通过[4 + 2]环加成进行的，而是在砷处发生亲电攻击，然后在螺环配合物[Mo{As(C4Me4)CRCRCO}(CO)2(η5-C5H5)]中加入羰基配体进行金属化。
{"title":"Electrophilic As-functionalisation of σ-arsolido complexes.","authors":"Ryan M Kirk, Anthony F Hill","doi":"10.1039/d4dt01371a","DOIUrl":"https://doi.org/10.1039/d4dt01371a","url":null,"abstract":"<p><p>The σ-arsolido complex [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) while iodomethane affords a mixture of [Me<sub>2</sub>AsC<sub>4</sub>Me<sub>4</sub>]I, [MoMe(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and the arsole complexes <i>cisoid</i>- and <i>transoid</i>-[MoI(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and <i>transoid</i>-[Mo{C(O)Me}(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], The arsole ligand in [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) is readily liberated by NaI in acetone to afford free MeAsC<sub>4</sub>Me<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)]. In a similar manner, the reaction of [Mo(AsC<sub>4</sub>Ph<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeI affords MeAsC<sub>4</sub>Ph<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], while [Mo{AsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeOTf affords [Mo{MeAsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf). The reaction of [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with activated alkynes (RCCR: R = CF<sub>3</sub>, CO<sub>2</sub>Me) does not proceed <i>via</i> [4 + 2] <i>cyclo</i>-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C<sub>4</sub>Me<sub>4</sub>)CRCRCO}(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)].</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141490040","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}
Alessandro Di Michele, Elisa Boccalon, Ferdinando Costantino, Maria Bastianini, Riccardo Vivani, Morena Nocchetti
Layered double hydroxides (LDH) are a class of layered solids applied in many application fields. The study on synthetic methods able to control the interlayer composition and morphology of LDH is an open issue. The urea method, that exploits the thermal decomposition of urea, is known for yielding highly crystalline LDH in carbonate form. This form is highly stable and, to replace carbonate ions with more easily exchangeable anions, a second step is required. In this work, we modified the urea method to obtain MgAl and ZnAl LDH in chloride or nitrate form through a one-step synthesis. The effect of the urea/(Al+M(II)) molar ratio (R), reaction time and metal salt concentrations were deeply investigated. We found that LDH in chloride and nitrate forms can be prepared from solutions of metal salts not exceeding 1M by adjusting R and maintaining the reaction time at 48 hours. The morphology of these products was found to depend on the R value and on the metal salts used in the synthesis. High R value and nitrate salts favoured the formation of sand-rose crystals, while chloride salts induced the formation of plate-like crystals. The crystal growth mechanism and the parameters influencing the morphology are discussed with reference to ZnAl LDH by monitoring the synthesis over time.
层状双氢氧化物（LDH）是应用于许多领域的一类层状固体。研究能够控制 LDH 层间成分和形态的合成方法是一个未决问题。众所周知，利用尿素热分解的尿素法可以生成碳酸盐形式的高结晶 LDH。这种形态高度稳定，要想用更易交换的阴离子取代碳酸根离子，还需要第二步。在这项工作中，我们对尿素法进行了改进，通过一步合成法获得了氯化物或硝酸盐形式的 MgAl 和 ZnAl LDH。我们深入研究了尿素/（Al+M(II)）摩尔比（R）、反应时间和金属盐浓度的影响。我们发现，通过调节 R 并将反应时间保持在 48 小时，可以从不超过 1M 的金属盐溶液中制备出氯化物和硝酸盐形式的 LDH。我们发现这些产物的形态取决于 R 值和合成中使用的金属盐。高 R 值和硝酸盐有利于沙玫瑰晶体的形成，而氯化物盐则会诱导板状晶体的形成。通过监测合成过程的时间，以 ZnAl LDH 为例讨论了晶体生长机制和影响形态的参数。
{"title":"Insight on the synthesis of LDH with urea method: morphology and intercalated anion control","authors":"Alessandro Di Michele, Elisa Boccalon, Ferdinando Costantino, Maria Bastianini, Riccardo Vivani, Morena Nocchetti","doi":"10.1039/d4dt01529k","DOIUrl":"https://doi.org/10.1039/d4dt01529k","url":null,"abstract":"Layered double hydroxides (LDH) are a class of layered solids applied in many application fields. The study on synthetic methods able to control the interlayer composition and morphology of LDH is an open issue. The urea method, that exploits the thermal decomposition of urea, is known for yielding highly crystalline LDH in carbonate form. This form is highly stable and, to replace carbonate ions with more easily exchangeable anions, a second step is required. In this work, we modified the urea method to obtain MgAl and ZnAl LDH in chloride or nitrate form through a one-step synthesis. The effect of the urea/(Al+M(II)) molar ratio (R), reaction time and metal salt concentrations were deeply investigated. We found that LDH in chloride and nitrate forms can be prepared from solutions of metal salts not exceeding 1M by adjusting R and maintaining the reaction time at 48 hours. The morphology of these products was found to depend on the R value and on the metal salts used in the synthesis. High R value and nitrate salts favoured the formation of sand-rose crystals, while chloride salts induced the formation of plate-like crystals. The crystal growth mechanism and the parameters influencing the morphology are discussed with reference to ZnAl LDH by monitoring the synthesis over time.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495701","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}
In this manuscript, a simple one-pot heat-up method has been used to prepare multi-component copper-tin-sulfur nanomaterials, including binary Cu1.94S, ternary Cu4SnS4, and Cu1.94S/Cu4SnS4 nanocrystals by varying the reaction temperature, reaction time, and the type of copper source. Post-synthetic ligand exchange (LE) has further been introduced to replace the long-chain ligands originated from 1-dodecanethiol. It has been found that the LE process not only changes the surface ligands but also significantly affects the crystal structure and optical properties of nanocrystals. After LE, the crystal structures of Cu1.94S and Cu4SnS4 transformed to Cu7S4 and Cu3SnS4, respectively, with the Cu1.94S/Cu4SnS4 nanocrystals showing the same trend. This phenomenon could be ascribe to the loss of Cu+ originating from the strong complexation of Cu+ and ammonia with the formation of [Cu(NH3)n]2+ ions under aerobic conditions. The proton nuclear magnetic resonance (1H NMR) has been used to characterize the ligands on the surface before and after LE, which further demonstrated that the -SH was replaced during LE. Meanwhile, the band gaps of the obtained nanocrystals after LE shows obvious shift in the near-infrared region due to the evolution of crystal structures. This study will provide useful guidance for the LE of nanocrystals and the application of copper-based sulfide nanomaterials in optoelectronics and other fields.
{"title":"Ligand Exchange Induced Crystal Structure and Morphology Evolution of Copper-Tin-Sulfur Binary and Ternary Compounds","authors":"Suqin Chen, Ying Xu, Yangyang Weng, Pengfei Lou, Xiaoyan Zhang, Ningzhong Bao","doi":"10.1039/d4dt00309h","DOIUrl":"https://doi.org/10.1039/d4dt00309h","url":null,"abstract":"In this manuscript, a simple one-pot heat-up method has been used to prepare multi-component copper-tin-sulfur nanomaterials, including binary Cu1.94S, ternary Cu4SnS4, and Cu1.94S/Cu4SnS4 nanocrystals by varying the reaction temperature, reaction time, and the type of copper source. Post-synthetic ligand exchange (LE) has further been introduced to replace the long-chain ligands originated from 1-dodecanethiol. It has been found that the LE process not only changes the surface ligands but also significantly affects the crystal structure and optical properties of nanocrystals. After LE, the crystal structures of Cu1.94S and Cu4SnS4 transformed to Cu7S4 and Cu3SnS4, respectively, with the Cu1.94S/Cu4SnS4 nanocrystals showing the same trend. This phenomenon could be ascribe to the loss of Cu+ originating from the strong complexation of Cu+ and ammonia with the formation of [Cu(NH3)n]2+ ions under aerobic conditions. The proton nuclear magnetic resonance (1H NMR) has been used to characterize the ligands on the surface before and after LE, which further demonstrated that the -SH was replaced during LE. Meanwhile, the band gaps of the obtained nanocrystals after LE shows obvious shift in the near-infrared region due to the evolution of crystal structures. This study will provide useful guidance for the LE of nanocrystals and the application of copper-based sulfide nanomaterials in optoelectronics and other fields.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495710","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}
Although molecular tetrahedral Ti-oxo species exhibit unique electronic and photochemical properties due to their discrete energy levels, which are different from those of anatase and rutile, such Ti-oxo species are generally unstable and readily transformed to amorphous/crystalline TiO2 (bulk phases, nanoparticles and clusters) via hydrolysis and condensation. Here, molecular Ti-oxo species were immobilised within mesoporous silica SBA-15 by grafting titanium(IV) oxyacetylacetonate using the surface silanol groups of SBA-15 as a scaffold, followed by chemical etching with dilute hydrochloric acid to form molecular TiO4 species. These Ti species mainly exist as isolated tetrahedrally coordinated structures, as was confirmed by diffuse reflectance UV−vis and Raman spectroscopy. The SBA-15-immobilised molecular TiO4 exhibited higher photocatalytic activity for H2 evolution from an aqueous methanol solution than conventional Ti-incorporated mesoporous silica (Ti-MCM-41) and reference TiO2 (P25).
{"title":"Stabilisation of molecular TiO4 species on the pore surface of mesoporous silica for photocatalytic H2 evolution","authors":"Hikaru Inada, Masashi Morita, Kazuyuki Maeda","doi":"10.1039/d4dt01610f","DOIUrl":"https://doi.org/10.1039/d4dt01610f","url":null,"abstract":"Although molecular tetrahedral Ti-oxo species exhibit unique electronic and photochemical properties due to their discrete energy levels, which are different from those of anatase and rutile, such Ti-oxo species are generally unstable and readily transformed to amorphous/crystalline TiO<small><sub>2</sub></small> (bulk phases, nanoparticles and clusters) via hydrolysis and condensation. Here, molecular Ti-oxo species were immobilised within mesoporous silica SBA-15 by grafting titanium(IV) oxyacetylacetonate using the surface silanol groups of SBA-15 as a scaffold, followed by chemical etching with dilute hydrochloric acid to form molecular TiO<small><sub>4</sub></small> species. These Ti species mainly exist as isolated tetrahedrally coordinated structures, as was confirmed by diffuse reflectance UV−vis and Raman spectroscopy. The SBA-15-immobilised molecular TiO<small><sub>4</sub></small> exhibited higher photocatalytic activity for H<small><sub>2</sub></small> evolution from an aqueous methanol solution than conventional Ti-incorporated mesoporous silica (Ti-MCM-41) and reference TiO<small><sub>2</sub></small> (P25).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495734","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}
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