In this contribution, we present the reactions of the o-carborane-based analogue of 9-bromo-9-borafluorene, a Lewis superacid, with diverse Lewis bases. A range of acid-base adducts, along with an intramolecular C–H activation product, were generated. All new compounds have been fully characterized.
{"title":"Reactivity study of Lewis superacidic carborane-based analogue of 9-bromo-9-borafluorene towards Lewis bases","authors":"Libo Xiang, Alexander Matler, Leibo Tan, Qing Ye","doi":"10.1039/d4dt01615g","DOIUrl":"https://doi.org/10.1039/d4dt01615g","url":null,"abstract":"In this contribution, we present the reactions of the o-carborane-based analogue of 9-bromo-9-borafluorene, a Lewis superacid, with diverse Lewis bases. A range of acid-base adducts, along with an intramolecular C–H activation product, were generated. All new compounds have been fully characterized.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444864","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}
Jonas Krieft, Beate Neumann, Georg Stammler, Norbert Werner Mitzel
The reactions of the Frustrated Lewis Pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetra¬chloro-ortho-¬benzo-quinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2∙2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.
受挫路易斯对 (F5C2)2SbCH2P(tBu)2 与氧、硫、硒和碲的反应产生了单氧化产物 (F5C2)2SbCH2P(E)(tBu)2（E = O、S、Se、Te）。这些缩醛加合物与四氯邻苯醌（邻氯苯醌）进一步氧化，得到了 (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl （CatCl = o-O2C6Cl4），其中 E = O、S、Se 时，中心为四元环杂环。在 E = Te 的情况下，消除碲元素可得到含有两个邻氯苯胺当量的氧化产物 (F5C2)2SbCH2P(tBu)2∙2CatCl，也可通过 (F5C2)2SbCH2P(tBu)2 与邻氯苯胺反应得到。通过核磁共振光谱和 X 射线结构分析对合成的化合物进行了表征，并根据锑原子氧化导致的路易斯酸度改变对其结构特性进行了分析。
{"title":"Oxidation-Dependent Lewis Acidity in Chalcogen Adducts of Sb/P Frustrated Lewis Pairs","authors":"Jonas Krieft, Beate Neumann, Georg Stammler, Norbert Werner Mitzel","doi":"10.1039/d4dt01591f","DOIUrl":"https://doi.org/10.1039/d4dt01591f","url":null,"abstract":"The reactions of the Frustrated Lewis Pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetra¬chloro-ortho-¬benzo-quinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2∙2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444940","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}
Synthesis and reactivity with carbon dioxide (CO2) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO2 activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)2(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC8 yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)2}n] 1-Sm. Addition of 1,2-dimethoxyethane (DME) to 1-Sm enabled isolation of the monomeric complex [Sm(Tp)2(DME)] 1-Sm(DME). Complex 1-Sm(DME) reduced CO2 to yield the oxalate-bridged dimeric Sm(III) complex [{Sm(Tp)2}2(μ-η2:η2-O2CCO2)] 2-Sm. The reactions of heteroleptic Ln(III) silylamide complexes [Ln(Tp)2(Nʹʹ)] (Ln = Y, Sm; Nʹʹ = N(SiMe3)2) with CO2 yielded monomeric Ln(III) silyloxides [Ln(Tp)2(OSiMe3)] 3-Ln and trimethylsilyl isocyanate (O=C=NSiMe3). Complexes 3-Ln are the first crystallographically characterised examples of Ln(III)–OSiMe3 bonds accessed via CO2 activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.
{"title":"Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes","authors":"Tajrian Chowdhury, Claire Wilson, Joy Farnaby","doi":"10.1039/d4dt01382d","DOIUrl":"https://doi.org/10.1039/d4dt01382d","url":null,"abstract":"Synthesis and reactivity with carbon dioxide (CO<small><sub>2</sub></small>) of divalent samarium in the <em>bis</em>-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO<small><sub>2</sub></small> activation and functionalisation by lanthanide silylamides in the <em>bis</em>-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)<small><sub>2</sub></small>(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC<small><sub>8</sub></small> yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)<small><sub>2</sub></small>}<small><sub><em>n</em></sub></small>] <strong>1-Sm</strong>. Addition of 1,2-dimethoxyethane (DME) to <strong>1-Sm</strong> enabled isolation of the monomeric complex [Sm(Tp)<small><sub>2</sub></small>(DME)] <strong>1-Sm(DME)</strong>. Complex <strong>1-Sm(DME)</strong> reduced CO<small><sub>2</sub></small> to yield the oxalate-bridged dimeric Sm(III) complex [{Sm(Tp)<small><sub>2</sub></small>}<small><sub>2</sub></small>(<em>μ</em>-<em>η</em><small><sup>2</sup></small>:<em>η</em><small><sup>2</sup></small>-O<small><sub>2</sub></small>CCO<small><sub>2</sub></small>)] <strong>2-Sm</strong>. The reactions of heteroleptic Ln(III) silylamide complexes [Ln(Tp)<small><sub>2</sub></small>(Nʹʹ)] (Ln = Y, Sm; Nʹʹ = N(SiMe<small><sub>3</sub></small>)<small><sub>2</sub></small>) with CO<small><sub>2</sub></small> yielded monomeric Ln(III) silyloxides [Ln(Tp)<small><sub>2</sub></small>(OSiMe<small><sub>3</sub></small>)] <strong>3-Ln</strong> and trimethylsilyl isocyanate (O=C=NSiMe<small><sub>3</sub></small>). Complexes <strong>3-Ln</strong> are the first crystallographically characterised examples of Ln(III)–OSiMe<small><sub>3</sub></small> bonds accessed <em>via</em> CO<small><sub>2</sub></small> activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444794","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}
Stefan Engel, Elias C. J. Gießelmann, Lars Schumacher, Yuemei Zhang, Frank Müller, Oliver Janka
Following recent investigation in the ternary system Sr–Al–Pt led to the discovery of SrAl5Pt3 which crystallizes in the orthorhombic YNi5Si3 type (Pnma) structure. Interestingly, only two more aluminum representatives, CeAl5Pt3 and EuAl5Pt3, have been reported to adopt this structure type. Therefore, we decided to investigate the existence range of compounds adopting the YNi5Si3 type structure. Besides the already known Sr, Ce and Eu members, the series could be extended to Ca, Y and La-Nd as well as Sm-Er. All compounds were synthesized from the elements and characterized by powder X-ray diffraction. While for CaAl5Pt3 and LaAl5Pt3 also the respective M2Al16Pt9 members were observed, the other compounds could be obtained either as X-ray pure materials or with small amounts of Al3Pt2 as side phase. The structure of ErAl5Pt3 could be refined from single crystal data, verifying that also the small rare-earth elements adopt the YNi5Si3 type structure. Selected members of the series were furthermore characterized by magnetization and susceptibility measurements. Since YAl5Pt3 could be obtained as phase pure material and exhibits no paramagnetic behavior it was investigated by 27Al MAS NMR investigations. Also, XPS measurements were conducted on this compound to gain an insight into the charge distribution. Finally, quantum-chemical calculations supported the NMR measurements and gave an insight into the chemical bonding and the charge distribution.
{"title":"Synthesis, Magnetic and NMR spectroscopic properties of the MAl5Pt3 series (M = Ca, Y, La-Nd, Sm-Er)","authors":"Stefan Engel, Elias C. J. Gießelmann, Lars Schumacher, Yuemei Zhang, Frank Müller, Oliver Janka","doi":"10.1039/d4dt01296h","DOIUrl":"https://doi.org/10.1039/d4dt01296h","url":null,"abstract":"Following recent investigation in the ternary system Sr–Al–Pt led to the discovery of SrAl5Pt3 which crystallizes in the orthorhombic YNi5Si3 type (Pnma) structure. Interestingly, only two more aluminum representatives, CeAl5Pt3 and EuAl5Pt3, have been reported to adopt this structure type. Therefore, we decided to investigate the existence range of compounds adopting the YNi5Si3 type structure. Besides the already known Sr, Ce and Eu members, the series could be extended to Ca, Y and La-Nd as well as Sm-Er. All compounds were synthesized from the elements and characterized by powder X-ray diffraction. While for CaAl5Pt3 and LaAl5Pt3 also the respective M2Al16Pt9 members were observed, the other compounds could be obtained either as X-ray pure materials or with small amounts of Al3Pt2 as side phase. The structure of ErAl5Pt3 could be refined from single crystal data, verifying that also the small rare-earth elements adopt the YNi5Si3 type structure. Selected members of the series were furthermore characterized by magnetization and susceptibility measurements. Since YAl5Pt3 could be obtained as phase pure material and exhibits no paramagnetic behavior it was investigated by 27Al MAS NMR investigations. Also, XPS measurements were conducted on this compound to gain an insight into the charge distribution. Finally, quantum-chemical calculations supported the NMR measurements and gave an insight into the chemical bonding and the charge distribution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444782","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}
NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(II) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of PdII/PdIV catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(II) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.
{"title":"An N-heterocyclic carbene-based pincer system of palladium and its versatile reactivity under oxidizing conditions.","authors":"Haobin Li, Bo Zhang, Rui Feng, Shuai Guo","doi":"10.1039/d4dt00980k","DOIUrl":"https://doi.org/10.1039/d4dt00980k","url":null,"abstract":"<p><p>NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(II) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of Pd<sup>II</sup>/Pd<sup>IV</sup> catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(II) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141441816","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}
Miсhael Olegovych Kalinkin, Dina Georgievna Kellerman, Nadezhda Ivanovna Medvedeva
The DFT method was used to predict the formation energies and quadrupole coupling constants CQ in a series of borophosphates: Li3BP2O8, Li2NaBP2O8, Na3BP2O8, Li2B3PO8, Na5B2P3O13, LiNa2B5P2O14 and Na3B6PO13 composed of different networks and different amounts of borate and phosphate units. The change in formation energies with increasing number of B atoms in this series is attributed to the multiplicity of boron sites and is explained by density of states calculations. The calculated CQ of 7Li, 23Na and 11B are compared with the coordination and distortion of polyhedra to elucidate the influence of local and more distant environments. As for CQ of 11B, it should be in the range of 0.26-0.36, 0.48-0.84 and ~ 1 MHz for a boron tetrahedral distortion index of 0.004-0.013, 0.015-0.019 and 0.033, respectively, whereas CQ ~ 3.0 MHz corresponds to boron in a triangular site. The obtained numerical relations make it possible to predict the quadrupole frequencies for these nuclei based only on their local environment, and vice versa, to propose structural models from NMR data. These results provide guidance for studying similar characteristics of other borophosphates, the structure of which varies depending on the initial reaction, composition and temperature.
{"title":"Ab initio study of stability and quadrupole coupling constants in borophosphates","authors":"Miсhael Olegovych Kalinkin, Dina Georgievna Kellerman, Nadezhda Ivanovna Medvedeva","doi":"10.1039/d4dt01429d","DOIUrl":"https://doi.org/10.1039/d4dt01429d","url":null,"abstract":"The DFT method was used to predict the formation energies and quadrupole coupling constants <em>C</em><small><sub>Q</sub></small> in a series of borophosphates: Li<small><sub>3</sub></small>BP<small><sub>2</sub></small>O<small><sub>8</sub></small>, Li<small><sub>2</sub></small>NaBP<small><sub>2</sub></small>O<small><sub>8</sub></small>, Na<small><sub>3</sub></small>BP<small><sub>2</sub></small>O<small><sub>8</sub></small>, Li<small><sub>2</sub></small>B<small><sub>3</sub></small>PO<small><sub>8</sub></small>, Na<small><sub>5</sub></small>B<small><sub>2</sub></small>P<small><sub>3</sub></small>O<small><sub>13</sub></small>, LiNa<small><sub>2</sub></small>B<small><sub>5</sub></small>P<small><sub>2</sub></small>O<small><sub>14</sub></small> and Na<small><sub>3</sub></small>B<small><sub>6</sub></small>PO<small><sub>13</sub></small> composed of different networks and different amounts of borate and phosphate units. The change in formation energies with increasing number of B atoms in this series is attributed to the multiplicity of boron sites and is explained by density of states calculations. The calculated <em>C</em><small><sub>Q</sub></small> of <small><sup>7</sup></small>Li, <small><sup>23</sup></small>Na and <small><sup>11</sup></small>B are compared with the coordination and distortion of polyhedra to elucidate the influence of local and more distant environments. As for <em>C</em><small><sub>Q</sub></small> of 11B, it should be in the range of 0.26-0.36, 0.48-0.84 and ~ 1 MHz for a boron tetrahedral distortion index of 0.004-0.013, 0.015-0.019 and 0.033, respectively, whereas <em>C</em><small><sub>Q</sub></small> ~ 3.0 MHz corresponds to boron in a triangular site. The obtained numerical relations make it possible to predict the quadrupole frequencies for these nuclei based only on their local environment, and vice versa, to propose structural models from NMR data. These results provide guidance for studying similar characteristics of other borophosphates, the structure of which varies depending on the initial reaction, composition and temperature.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444857","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}
A novel lysosome-targeted photosensitizer/photoredox catalysis based on cyclometalated Ir(III) complex IrL has been designed and synthesized, which exhibited excellent phosphorescence properties and the ability to generate single oxygen (1O2) and photocatalytically oxidize 1,4-dihydronicotinamide adenine dinucleotide (NADH) under light irradiation. Most importantly, the aforementioned activities are significantly enhanced due to protonation under acidic conditions, which make them highly attractive in light-activated tumor therapy, especially for acidic lysosomes and tumor microenvironments. The photocytotoxicity of IrL and the mechanism of cell death have been investigated. Additionally, the tumor-killing ability of IrL under light irradiation was evaluated using a 4T1 tumor-bearing mice model. This work provides a strategy for the development of lysosome-targeted photosensitizer/photoredox catalysis to overcome hypoxic tumors.
{"title":"Lysosome-targeted Cyclometalated Ir(III) Complexes as Photosensitizer/Photoredox Catalysis for Cancer Therapy","authors":"Jiaxi Ru, Yu Chen, Chao Liang, Manchang Kou, Xiao-Liang Tang","doi":"10.1039/d4dt01345j","DOIUrl":"https://doi.org/10.1039/d4dt01345j","url":null,"abstract":"A novel lysosome-targeted photosensitizer/photoredox catalysis based on cyclometalated Ir(III) complex IrL has been designed and synthesized, which exhibited excellent phosphorescence properties and the ability to generate single oxygen (1O2) and photocatalytically oxidize 1,4-dihydronicotinamide adenine dinucleotide (NADH) under light irradiation. Most importantly, the aforementioned activities are significantly enhanced due to protonation under acidic conditions, which make them highly attractive in light-activated tumor therapy, especially for acidic lysosomes and tumor microenvironments. The photocytotoxicity of IrL and the mechanism of cell death have been investigated. Additionally, the tumor-killing ability of IrL under light irradiation was evaluated using a 4T1 tumor-bearing mice model. This work provides a strategy for the development of lysosome-targeted photosensitizer/photoredox catalysis to overcome hypoxic tumors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444823","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}
Jianbo Xiong, Qing Li, Xiaojuan Tan, Xue Guo, Kaihui Li, Qiaolin Luo, Yao Chen, Xiao-Lan Tong, Bing Na, Ming Zhong
ZIF-67 derived nitrogen and cobalt doped carbon enfolded silicon (C@Si) nanoparticles anchored on the 2D MXene layers was constructed for boosting lithium-ion batteries (LIBs). The heterostructure anode demonstrates a high initial discharge capacity of 3021 mAh g−1 at 0.2 A g−1, retaining outstanding cycling stability with a reversible capacity of 520 mAh g−1 at 2000 mA/g with the coulombic efficiency remained above 97% after 500 cycles. The introduced Ti3C2 nanosheets and the cobalt doped carbon can not only contribute the interfacial transfer of Li+ and electron, but also buffer the volume expansion of Si.
在二维 MXene 层上锚定 ZIF-67 衍生的氮和钴掺杂碳包覆硅 (C@Si) 纳米粒子，用于增强锂离子电池 (LIB)。该异质结构阳极在 0.2 A g-1 条件下的初始放电容量高达 3021 mAh g-1，在 2000 mA/g 条件下的可逆容量为 520 mAh g-1，500 次循环后的库仑效率仍保持在 97% 以上，并保持了出色的循环稳定性。引入的 Ti3C2 纳米片和掺钴碳不仅能促进 Li+ 和电子的界面转移，还能缓冲硅的体积膨胀。
{"title":"Confinement of ZIF-67 derived N, Co-Doped C@Si on 2D MXene for Enhanced Lithium Storage","authors":"Jianbo Xiong, Qing Li, Xiaojuan Tan, Xue Guo, Kaihui Li, Qiaolin Luo, Yao Chen, Xiao-Lan Tong, Bing Na, Ming Zhong","doi":"10.1039/d4dt01314j","DOIUrl":"https://doi.org/10.1039/d4dt01314j","url":null,"abstract":"ZIF-67 derived nitrogen and cobalt doped carbon enfolded silicon (C@Si) nanoparticles anchored on the 2D MXene layers was constructed for boosting lithium-ion batteries (LIBs). The heterostructure anode demonstrates a high initial discharge capacity of 3021 mAh g−1 at 0.2 A g−1, retaining outstanding cycling stability with a reversible capacity of 520 mAh g−1 at 2000 mA/g with the coulombic efficiency remained above 97% after 500 cycles. The introduced Ti3C2 nanosheets and the cobalt doped carbon can not only contribute the interfacial transfer of Li+ and electron, but also buffer the volume expansion of Si.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439787","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 development of heteroatom dual-doped porous carbon frameworks with uniform doping is highly desirable for achieving highly efficient oxygen reduction reaction (ORR) activity, due to their tunable chemical and electronic structures. Herein, porous covalent triazine-based frameworks (CTFs) incorporating nitrogen/chorine dual-doped porous carbon networks were fabricated by selecting 1,3-bis(4-cyanophenyl) imidazolium chloride as a building block, in a facile and controllable way via a bottom-up strategy. The resulting nitrogen/chorine dual-doped catalyst CCTF-700 exhibits the excellent ORR performance with a more positive onset and half-wave potential (0.85 V vs. RHE), higher diffusion-limited current density and significantly improved stability in comparison with the benchmark commercial 20 wt% Pt/C catalyst. It is worth to mention that CCTF-700 possesses one of the best ORR performance among all the reported metal-free electrocatalysts under alkaline condition. This work paves the way for a controllable and reliable strategy to craft highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.
掺杂均匀的杂原子双掺杂多孔碳框架具有可调的化学和电子结构，因此要实现高效的氧还原反应（ORR）活性，开发这种框架是非常理想的。在此，研究人员选择 1,3-双（4-氰基苯基）氯化咪唑作为构筑基块，通过自下而上的策略，以简便、可控的方式制备了包含氮/氯碱双掺杂多孔碳网络的多孔共价三嗪基框架（CTFs）。与基准商用 20 wt% Pt/C 催化剂相比，氮/络氨酸双掺杂催化剂 CCTF-700 表现出优异的 ORR 性能，起始电位和半波电位（0.85 V vs. RHE）更正，扩散限制电流密度更高，稳定性显著提高。值得一提的是，CCTF-700 是所有已报道的碱性条件下无金属电催化剂中 ORR 性能最好的催化剂之一。这项工作为采用可控、可靠的策略制备用于能源转换的高效杂原子双掺杂碳催化剂铺平了道路。
{"title":"Boosting Oxygen Reduction Activity of Non-metallic Catalysts via Geometric and Electronic Engineering through Nitrogen and Chlorine Dual-Doping","authors":"Dong-Li Meng, Taotao Liu, Minghui Wu, Jing-Wen He, Shaowu Du, Yuan-Biao Huang","doi":"10.1039/d4dt01519c","DOIUrl":"https://doi.org/10.1039/d4dt01519c","url":null,"abstract":"The development of heteroatom dual-doped porous carbon frameworks with uniform doping is highly desirable for achieving highly efficient oxygen reduction reaction (ORR) activity, due to their tunable chemical and electronic structures. Herein, porous covalent triazine-based frameworks (CTFs) incorporating nitrogen/chorine dual-doped porous carbon networks were fabricated by selecting 1,3-bis(4-cyanophenyl) imidazolium chloride as a building block, in a facile and controllable way via a bottom-up strategy. The resulting nitrogen/chorine dual-doped catalyst CCTF-700 exhibits the excellent ORR performance with a more positive onset and half-wave potential (0.85 V vs. RHE), higher diffusion-limited current density and significantly improved stability in comparison with the benchmark commercial 20 wt% Pt/C catalyst. It is worth to mention that CCTF-700 possesses one of the best ORR performance among all the reported metal-free electrocatalysts under alkaline condition. This work paves the way for a controllable and reliable strategy to craft highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439850","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}
Rahul Chauhan, Govinda R. Navale, Saakshi Saini, Abhishek Panwar, Prashant Kukreti, Rajat Saini, Partha Roy, Kaushik Ghosh
The spontaneous aggregation of infectious or misfolded forms of prion protein is known to be responsible for neurotoxicty in brain cells which ultimately leads to the progression of prion disorders. Bovine spongiform encephalophathy (BSE) in animals and Creutzfeldt-Jakob disease (CJD) in humans are glaring examples in this regard. Square-planar complexes with labile ligands and indole-based compounds found to be efficiently inhibitory against protein aggregation. Herein, we report the synthesis of an indole-based cyclometallated palladium complex. The ligand and complex were characterized by various spectroscopic techniques such as UV-visible, NMR, IR, and HRMS. The molecular structure of the complex was confirmed by single-crystal X-ray crystallography. The interaction of the complex with the PrP106-126 were studied using UV-visible spectroscopy, CD spectroscopy, MALDI-TOF MS, and docking. The inhibition effects of complex on the PrP106-126 aggregation, fibrillization and amyloid formation phenomena were analysed through ThT assay, CD, TEM and AFM. The effect of the complex on the aggregation process of PrP106-126 were determined kinetically through ThT assay. The complex presented high binding affinity with the peptide and influenced peptide’s conformation and aggregation in different mode of binding. Further, the MTT assay on the neuronal HT-22 cells showed considerable protective properties of the complex against PrP106-126 mediated cytotoxicity. The findings suggest that the compound influences the peptide aggregation in different ways, and the anti-aggregation action is primarily associated with the metal’s physicochemical properties and the reactivity rather than the ligand. As a result, we propose that this compound be investigated as a potential therapeutic molecule in metallo-pharmaceutical research to treat prion disease (PD).
{"title":"Modulation of aggregation of human prion protein PrP106-126 by indole-based cyclometallated palladium complex","authors":"Rahul Chauhan, Govinda R. Navale, Saakshi Saini, Abhishek Panwar, Prashant Kukreti, Rajat Saini, Partha Roy, Kaushik Ghosh","doi":"10.1039/d4dt00704b","DOIUrl":"https://doi.org/10.1039/d4dt00704b","url":null,"abstract":"The spontaneous aggregation of infectious or misfolded forms of prion protein is known to be responsible for neurotoxicty in brain cells which ultimately leads to the progression of prion disorders. Bovine spongiform encephalophathy (BSE) in animals and Creutzfeldt-Jakob disease (CJD) in humans are glaring examples in this regard. Square-planar complexes with labile ligands and indole-based compounds found to be efficiently inhibitory against protein aggregation. Herein, we report the synthesis of an indole-based cyclometallated palladium complex. The ligand and complex were characterized by various spectroscopic techniques such as UV-visible, NMR, IR, and HRMS. The molecular structure of the complex was confirmed by single-crystal X-ray crystallography. The interaction of the complex with the PrP106-126 were studied using UV-visible spectroscopy, CD spectroscopy, MALDI-TOF MS, and docking. The inhibition effects of complex on the PrP106-126 aggregation, fibrillization and amyloid formation phenomena were analysed through ThT assay, CD, TEM and AFM. The effect of the complex on the aggregation process of PrP106-126 were determined kinetically through ThT assay. The complex presented high binding affinity with the peptide and influenced peptide’s conformation and aggregation in different mode of binding. Further, the MTT assay on the neuronal HT-22 cells showed considerable protective properties of the complex against PrP106-126 mediated cytotoxicity. The findings suggest that the compound influences the peptide aggregation in different ways, and the anti-aggregation action is primarily associated with the metal’s physicochemical properties and the reactivity rather than the ligand. As a result, we propose that this compound be investigated as a potential therapeutic molecule in metallo-pharmaceutical research to treat prion disease (PD).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439856","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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