Dalton Transactions最新文献

{"title":"Three-Dimensional Hollow ZnS/MXene Heterostructure with Stable Ti-O-Zn Bonding for Enhanced Lithium-Ion Storage","authors":"Rujia Zou, Wei Yang, Wenqing Wang, Shidi Huang, Mengluan Gao, Fuming Weng","doi":"10.1039/d4dt03381g","DOIUrl":"https://doi.org/10.1039/d4dt03381g","url":null,"abstract":"An effective way to improve the cycling performance of metal sulfide materials is to blend them with conductive materials. In this paper, three-dimensional (3D) hollow MXene/ZnS heterostructures (ZnSMX) were prepared via a two-step process involving hydrothermal and template methodology. The formation of Ti-O-Zn bonds enables the firm bonding between ZnS nanoparticles and the MXene substrate at heterogeneous interfaces, which can act as \"electron bridges\" to facilitate electron and charge transfer. Most importantly, 3D hollow ZnSMX not only enhances the conductivity of ZnS, enabling rapid charge transfer, but also effectively restacking of MXene nanosheets to maintain structural stability during the charge/discharge process. More importantly, the 3D macroporous structure provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites, and thus, boosts the excellent storage performances in lithium-ion batteries applications. The 3D ZnSMX exhibited a high capacity of 782.1 mAh g-1 at 1 A g-1 current, excellent cycling stability (providing a high capacity of 1027.8 mA h g-1 after 350 cycles at 2 A g-1), and excellent rate performance. This indicates that 3D ZnS/MXene heterostructure has the potential to be a highly promising anode material for high-multiplication lithium-ion batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050589","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}

{"title":"Bis(formazanate) Iron(II) Complexes as Cathode Material for One-Compartment H2O2 Fuel Cell","authors":"Sunita Birara, Moumita Majumder, Ramesh K. Metre","doi":"10.1039/d4dt03253e","DOIUrl":"https://doi.org/10.1039/d4dt03253e","url":null,"abstract":"In this paper, we describe the synthesis of two six-coordinate, pseudo(octahedral) bis(formazanate) Fe(II) complexes based on new redox-active benzothiazole substituted formazanate ligands. Complexes [Fe<small>^II</small>(L1)<small>₂</small>], <strong>1</strong> and [Fe<small>^II</small>(L2)<small>₂</small>], <strong>2</strong> were synthesized by reacting <em>1-(benzothiazol-2-yl)-5-phenyl-3-(pyren-1-yl)formazan</em> (L1H) and <em>1-(benzothiazol-2-yl)-5-(2-benzoyl-4-chlorophenyl)-3-phenylformazan</em> (L2H) respectively with the appropriate Fe(II) precursors at room temperature. The molecular structure of both the bis(formazanate) iron complexes has been established using Single-Crystal XRD, and other characterization methods were utilized to characterize these complexes further, as well as the newly synthesized ligands. Furthermore, the cyclic voltammetry of these compounds is documented, revealing that both complexes may undergo electrochemical reductions to create anionic and dianionic species. These complexes were further employed as the cathode of one-compartment membrane-less H<small>₂</small>O<small>₂</small> fuel cells, operating in 0.5 M H<small>₂</small>O<small>₂</small> with nickel foam serving as the anode. The maximum power densities achieved by the designed H<small>₂</small>O<small>₂</small> fuel cell for complexes <strong>1</strong> and <strong>2</strong> were 1.88 mW cm<small>^-2</small> and 3.08 mW cm<small>^-2</small>, respectively. This study demonstrates the significant potential for investigating formazanate-based compounds in the development of cathode materials for H<small>₂</small>O<small>₂</small> fuel cells.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"84 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050592","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}

{"title":"Homochiral Dy2 zero-field single-molecule magnets derived from axial chiral ligands (R)/(S)-octahydro-1,1'-bi-2-naphthyl phosphate","authors":"Cai-Ming Liu, Xiang Hao, Yi-Quan Zhang","doi":"10.1039/d4dt03408b","DOIUrl":"https://doi.org/10.1039/d4dt03408b","url":null,"abstract":"The construction of homochiral zero-field single-molecule magnets (SMMs), especially with axial chiral ligands, remains a great challenge. Herein the first examples of homochiral Dy(III) Schiff base complexes based on axial chiral ligands (<em>R</em>)/(<em>S</em>)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthyl phosphate (<em>R</em>-HL/<em>S</em>-HL), [Dy<small>₂</small>(<em>R</em>-L/<em>S</em>-L)<small>₂</small>(L<small>_Schiff</small>)<small>₂</small>(H<small>₂</small>O)(MeOH)]·2MeOH·CH<small>₂</small>Cl<small>₂</small>·2MeCN·2H<small>₂</small>O (<em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong>) [H<small>₂</small>L<small>_Schiff</small> = (E)-N'-(5-fluoro-2-hydroxybenzylidene)pyrazine-2-carbohydrazide], were synthesized at room temperature, which show ferromagnetic coupling, and perform as zero-field SMMs, with a <em>U</em><small>_eff</small>/<em>k</em> value of 61 K at 0 Oe. Ab initio calculations were used to explain their magnetic interaction and magnetic relaxation properties. Furthermore, the magnetic circular dichroism (MCD) spectra of <em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong> revealed that they display obvious magneto-optical effects.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050590","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}

{"title":"Low coordinate potassium alkoxide - an efficient trap for arenes: the role of ηn non-covalent bonding in substrate activation for C-H bond metalation","authors":"Alexander A. Trifonov, Alexander N Selikhov, Yulia Nelyubina, Rinat R. Aysin","doi":"10.1039/d4dt03326d","DOIUrl":"https://doi.org/10.1039/d4dt03326d","url":null,"abstract":"Metalation of bulky tris(2-(piperidin-1-yl-methyl)phenyl)methanol [(C5H10N)CH2C6H4-o]3COH with (Me3Si)2NK in Et2O results in a dimeric potassium alkoxide {[(C5H10N)CH2C6H4-o]3C(μ2-O)K(Et2O)}2(1). Et2O molecule can be removed from the K+ coordination sphere affording coordinatively unsaturated alkoxide species which readily traps π-donor molecules. In the presence of arene excess the reactions result in ηn-π-complexes retaining in crystal state a dimeric core {[(C5H10N)CH2C6H4-o]3C(μ2-O)K(ηn-arene)}2 (arene = C6H6 (2), CH3C6H5 (3), C10H8 (4)). With C6H5OMe and C6H5NMe2 molecules containing competing n- and π-donating sites the reactions proceed differently: the former coordinates to K+ through an oxygen lone pair resulting in {[(C5H10N)CH2C6H4-o]3C(μ2-O)K(κ1-O(Me)C6H5}2 (5) while for the latterπ-arene interaction turns out to be preferable {[(C5H10N)CH2C6H4-o]3C(μ2-O)K(η2-C6H5NMe2)}2 (6). The reactions with equimolar amounts of benzene or thiophene afford coordination polymers [{[(C5H10N)CH2C6H4-o]3C(μ2-O)K}2(μ-C6H6)]n (7) and [{[(C5H10N)CH2C6H4-o]3C(μ2-O)K}2(μ-C4H4S)]n (8), in which benzene and thiophene molecules are μ-bridging two K+ ions. The treatment of {[(C5H10N)CH2C6H4-o]3C(μ2-O)K(η2-CH3C6H5))}2 with Me3SiCH2Li or n-BuLi (1.2 eq) in hexane at 20 °C results in the facile metalation of Me-group of toluene, the formation of [PhCH2K]n and lithium alkoxide . This model reaction provides a deeper insight into the probable mechanism of metalation of CH bonds under Lochmann–Schlosser superbasic conditions, the role and the nature of the synergistic effect of two metals. The calculations and QTAIM analysis were performed for 1-8 and model molecules as well.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050603","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}

{"title":"Metal-ligand and Hydrogen Bonding in the Active Site of Fe(III)-, Mn(III)- and Co(III)-myoglobins","authors":"Marek Freindorf, Elfi Kraka","doi":"10.1039/d4dt03246b","DOIUrl":"https://doi.org/10.1039/d4dt03246b","url":null,"abstract":"We investigated in this work the strength of metal–ligand bonding in complexes formed between Fe(III)- , Mn(III)- and Co(III)-myoglobin and methanol, water, nitrite, and azide, serving as neutral and ionic prototype ligands, for the ε and δ protonation forms of the myoglobin distal histidine. In total, 24 complexes and 12 associated gas phase models were investigated combining a QM/MM protocol with our local vibrational mode analysis at the PBE0/6-31g(d,p)/AMBER level of theory. According to our results, complexes with methanol and water ligands form weaker metal–ligand bonds than those with nitrite and azide ligands. Furthermore, the strength of the metal–ligand bonds depends on the protonation form of the distal histidine. Among the three metals investigated in this study, Fe, the metal found in native myoglobin, turned out to be the most versatile candidate, providing the broadest range of metal–ligand bond strengths. We also analyzed potential hydrogen bonds formed between the ligand and the distal histidine of the heme pocket. The ε tautomer of histidine forms weaker O· · · H type hydrogen bonds whereas the δ tautomer forms stronger N· · · H type hydrogen bonds. Overall, our findings identify the strength of both metal–ligand and hydrogen bonds (fully captured by our local vibrational mode analysis) as a key parameter determining the catalytic activity and function of myoglobins This is particularly relevant when considering neutral versus ionic ligands and other metals such as Mn or Co as alternatives to Fe. The insights gained through our investigation offer valuable guidance for strategically fine-tuning existing artificial myoglobins and designing new, versatile variants. We hope that our QM/MM - local mode analysis protocol will become a valuable addition to the research community’s toolkit.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044311","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}

{"title":"Synthesis, structures, and magnetic properties of alkali metal manganese(III) fluorophosphates containing low-dimensional <i>S</i> = 2 spin structures.","authors":"Xiedong Cheng, Feifan Li, Qingqing Huang, Laura C J Pereira, Rui Cui, Yaping Li, Minfeng Lü","doi":"10.1039/d4dt02768j","DOIUrl":"https://doi.org/10.1039/d4dt02768j","url":null,"abstract":"<p><p>Five alkali metal manganese(III) fluorophosphates, K₂Mn(PO₃F)F₃ (I), Rb₂Mn(PO₃F)F₃ (II), Rb₂Mn₂(PO₃F)(PO₄)F₃ (III), Rb₃Mn₃(PO₃F)₂(PO₄)F₅ (IV), and CsMn(PO₃F)F₂ (V), were successfully synthesized using a hydrothermal method. The monofluorophosphate anion (PO₃F)^2- groups work as \"chemical scissors\" to promote low-dimensional spin structures with the aid of alkali metal cations. I and II had an <i>S</i> = 2 uniform chain structure formed by corner-sharing <i>trans</i>-MnO₂F₄ octahedra. III contained a quasi one-dimensional <i>S</i> = 2 spin chain composed of <i>trans</i>-MnO₄F₂ octahedra and <i>trans</i>-MnO₂F₄ octahedra through vertex-sharing fluorine atoms running along the [1-10] direction, whereas V exhibited a zigzag <i>S</i> = 2 spin chain built from the <i>facial</i>-MnO₃F₃ octahedron. In contrast, IV constitutes weakly coupled <i>S</i> = 2 spin trimers, where the three-dimensional (3D) framework contains two-dimensional {Mn₃O₄F₄(PO₃F)₂}^2- layers formed by trinuclear Mn-octahedral units <i>via</i> corner-sharing fluorine atoms separated by PO₃F tetrahedra. Magnetic measurements confirmed that I and II possess antiferromagnetic (AFM) long-range ordering at low temperature, with intrachain exchange couplings <i>J</i>_intra/<i>k</i>_B = -12.1(1) K for I and <i>J</i>_intra/<i>k</i>_B = -8.1(2) K for II. The magnetic behaviour of IV was very complex, with three successive magnetic transitions owing to weak AFM coupling among <i>S</i> = 2 spin trimers. V shows an alternating <i>S</i> = 2 one-dimensional (1D) chain with canted AFM ordering at 16.5 K.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044961","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}

{"title":"Nickel(II) complexes with covalently attached quinols rely on ligand-derived redox couples to catalyze superoxide dismutation","authors":"Robert Boothe, Julian Oppelt, Alicja Franke, Jamonica L. Moore, Andrea Squarcina, Achim Zahl, Laura Senft, Ina Kellner, Akudo L. Awalah, Alisabeth Bradford, Segun V. Obisesan, Dean D. Schwartz, Ivana Ivanović-Burmazović, Christian R. Goldsmith","doi":"10.1039/d4dt03331k","DOIUrl":"https://doi.org/10.1039/d4dt03331k","url":null,"abstract":"Although nickel is found in the active sites of a class of superoxide dismutase (SOD), nickel complexes with non-peptidic ligands normally do not catalyze superoxide degradation, and none has displayed activity comparable to those of the best manganese-containing SOD mimics. Here, we find that nickel complexes with polydentate quinol-containing ligands can exhibit catalytic activity comparable to those of the most efficient manganese-containing SOD mimics. The nickel complexes retain a significant portion of their activity in phosphate buffer and under operando conditions and rely on ligand-centered redox processes for catalysis. Although nickel SODs are known to cycle through Ni(<small>II</small>) and Ni(<small>III</small>) species during catalysis, cryo-mass spectrometry studies indicate that the nickel atoms in our catalysts remain in the +2 oxidation state throughout SOD mimicry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"188 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044313","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}

{"title":"Copper(III) organometallic complexes of non (anti)aromatic and aromatic doubly N-confused porphyrinoids: syntheses and characterization","authors":"Harapriya Rath, Anirban Panua, Gunasekaran Velmurugan, Peter Comba","doi":"10.1039/d4dt03265a","DOIUrl":"https://doi.org/10.1039/d4dt03265a","url":null,"abstract":"Retrosynthetically designed and synthesis of three unprecedented doubly N-confused porphyrinoids with tunable aromaticity are reported. Controlled modification of types of oxidants (chloranil vs. DDQ) has led to the isolation of cross-conjugated doubly N-confused porphyrinoid 7 (upon chloranil oxidation) and Hϋckel aromatic porphyrinoid 8, while DDQ oxidation has led to the 16  Hϋcckel-antiaromatic porphyrinoid 9. All three hybrid N-confused porphyrinoids 7-9 have been thoroughly characterized via solution state spectroscopic measurements and in-depth DFT studies. While 7 and 8 could form respective Cu(III) organometallic complexes, porphyrinoid 9 remained unsusceptible to Cu metallation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"114 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044838","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}

{"title":"An isolable boron-centered radical anion stabilized by a carbazole moiety","authors":"Ningning Yuan, Tingchun Zhu, Jianping Ma, Yunsheng Xue, Yirui Liu","doi":"10.1039/d4dt03314k","DOIUrl":"https://doi.org/10.1039/d4dt03314k","url":null,"abstract":"The isolation of a stable persistent carbazole-stabilized boron-centered monoradical anion <strong>1</strong>˙<small>⁻</small>, which has a high spin density at the B atom, has been reported. It is characterized using the crystal structure and UV-vis absorption spectrum, as well as electron paramagnetic resonance spectroscopy. Interestingly, the B–N bond was activated by the boron-centered radical anion <strong>1</strong>˙<small>⁻</small>, which had not been reported before.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044314","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}

{"title":"Polydopamine-coated cerium oxide core-shell nanoparticles for efficient and non-damaging chemical-mechanical polishing","authors":"Xiaohai He, Bo Gao, Qingyuan Wu, Chengrui Xin, Junjie Xue, Fangwei Lu, Xin-Ping Qu, Simin Li, Fan Zhang, Hui Shen","doi":"10.1039/d4dt03546a","DOIUrl":"https://doi.org/10.1039/d4dt03546a","url":null,"abstract":"Chemical mechanical polishing (CMP) represents one of the most important steps in the manufacturing of integrated circuits and high surface quality is always required for the CMP processes of shallow trench isolation (STI) structures. Herein, a new series of polydopamine (PDA)-coated cerium oxide core-shell nanoparticles has been developed as efficient and non-damaging abrasives for CMP of SiO2 on the surface of silicon wafers. The composite abrasives with the structure of SiO2@CeO2@PDA have been fabricated in a simple manner and thoroughly characterized using scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The SiO2 core enhances the content of Ce3+ in the abrasives, while the water-soluble PDA layer facilitates the interaction between the abrasives and SiO2 dielectrics. As a result, the wafers polished by SiO2@CeO2@PDA not only achieved a high polishing rate but also exhibited a high surface quality (Ra = 0.109). This study not only presents a new efficient and non-damaging type of cerium oxide abrasives for CMP, but also highlights the potential of the surface coordination strategy in the fabrication of advanced abrasives for the manufacturing of integrated circuits.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044315","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}