Dalton Transactions最新文献

{"title":"A bentonite/ZIF-8 derived ZnO photocatalyst for the effective elimination of a mixture of endocrine disruptors under simulated solar light: estrogenicity mitigation","authors":"Pedro César Quero-Jiménez, Aracely Hernández-Ramírez, Giselle Gomes, Jorge Luis Guzmán-Mar, Daniele Maia-Bila, Laura Hinojosa-Reyes","doi":"10.1039/d5dt00154d","DOIUrl":"https://doi.org/10.1039/d5dt00154d","url":null,"abstract":"The hybrid bentonite/ZnO composites based on the metal–organic framework (MOF) ZIF-8 were synthesized by a microwave method using 2-methylimidazole and zinc nitrate, and incorporating natural bentonite (5, 15, and 25 wt%) followed by thermal treatment at 550 °C. The as-prepared materials were characterized for their crystal structure, morphology, composition, surface chemical states, textural and optical properties. The photocatalytic activity of the ZnO/bentonite composites was evaluated in the degradation of a mixture solution of endocrine disruptors (EDCs) (bisphenol A, propylparaben, and 17α-ethinylestradiol, 5 mg L<small>⁻¹</small> each) at pH = 7 under simulated solar light. The material characterization showed that incorporating bentonite into ZnO increased the specific surface area, facilitated the formation of oxygen vacancies, and decreased the recombination rate of <em>e</em><small>⁻</small>/<em>h</em><small>⁺</small> pairs compared to ZnO. The solar photocatalytic activity revealed that bentonite 15 wt%/ZIF-8 derived ZnO composite showed enhanced photocatalytic activity compared to ZIF-8 derived ZnO, allowing the total degradation and 61.26% mineralization of the EDC mixture in 240 min. Furthermore, the effluent showed a decrease in estrogenic activity by the end of the photocatalytic process, with no by-products formed that present estrogenic activity. The bentonite/ZIF-8 derived ZnO composite is proposed as an alternative ZnO-based catalyst that effectively removes the EDC compounds from aqueous media.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758590","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, structure, and properties of antiaromatic PVO complexes of triphyrins(2.1.1)","authors":"Akrti Sharma, Mangalampalli Ravikanth","doi":"10.1039/d5dt00221d","DOIUrl":"https://doi.org/10.1039/d5dt00221d","url":null,"abstract":"A series of antiaromatic stable P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O complexes of &lt;em&gt;meso&lt;/em&gt;-tetra(&lt;em&gt;p&lt;/em&gt;-tolyl) triphyrin(2.1.1) and its β-substituted derivatives were synthesized in 38–48% yields by treating an appropriate aromatic free base triphyrin(2.1.1) with PCl&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt; in toluene/Et&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;N at reflux for 4–6 h. During the reaction, 14π aromatic &lt;em&gt;meso&lt;/em&gt;-tetra(&lt;em&gt;p&lt;/em&gt;-tolyl) triphyrin(2.1.1) is reduced to a 16π macrocycle and complexes with P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O to form antiaromatic P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O complexes of &lt;em&gt;meso&lt;/em&gt;-tetra(&lt;em&gt;p&lt;/em&gt;-tolyl) triphyrins(2.1.1). The X-ray structure obtained for one of the P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) complexes revealed that unlike the almost planar structure of free base &lt;em&gt;meso&lt;/em&gt;-tetraaryl triphyrin(2.1.1), P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) was highly distorted and adopted a domed structure with P(&lt;small&gt;V&lt;/small&gt;) placed at a distance of 0.927 Å above the mean plane defined by the four &lt;em&gt;meso&lt;/em&gt;-carbon atoms. NMR studies indicated the paratropic ring current effect in the P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) complexes and the outer β-pyrrole protons which appear in the downfield region of 7.50–8.20 ppm in free base triphyrin(2.1.1) experienced significant upfield shifts and appeared in the region of 3.50–4.50 ppm in P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) complexes, supporting the switching of aromatic 14π free base triphyrin(2.1.1) to antiaromatic 16π P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) complexes. The P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O triphyrin(2.1.1) complexes show one intense absorption band in the 300–350 nm region and an antiaromatic characteristic broad band in the lower energy region of 450–1000 nm. The electrochemical studies revealed that the P&lt;small&gt;&lt;sup&gt;V&lt;/sup&gt;&lt;/small&gt;&lt;img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/&gt;O ","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"97 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758068","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, electronic and photophysical investigations of ruthenium(II)-centred heterometallic Kuratowski complexes which feature redox-active metal centres","authors":"Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Binh Minh Nguyen, Wolfgang Brütting, Dirk Volkmer","doi":"10.1039/d5dt00088b","DOIUrl":"https://doi.org/10.1039/d5dt00088b","url":null,"abstract":"We present the synthesis and comprehensive characterization of a series of complexes belonging to the Kuratowski (K<small>_3,3</small>) family. These are pentanuclear {Ru<small>^II</small>M<small>₄</small>} complexes (M = Co<small>²⁺</small>, Ni<small>²⁺</small>, Zn<small>²⁺</small>) which were prepared by employing a directed two-step synthesis facilitated by the recently published [Ru<small>^II</small>(Me<small>₂</small>bta)<small>₂</small>(Me<small>₂</small>btaH)<small>₄</small>] precursor complex (Me<small>₂</small>btaH = 5,6-dimethyl-1,2,3-benzotriazole). The pentanuclear Kuratowski complexes showcase a unique combination of photo-active ruthenium with redox-active metal centres. The μ<small>₃</small>-bridging 1,2,3-triazolate ligands in these complexes facilitate electronic coupling between the metal centers, as revealed through electrochemical and photophysical studies. Comparisons with {Ru<small>^II</small>Zn<small>₄</small>} and {Ru<small>^II</small>Cu<small>₄</small>} Kuratowski compounds reveal that Co(<small>II</small>) significantly influences both the Ru(<small>II</small>/<small>III</small>) redox step and the position of the MLCT (metal-to-ligand charge transfer) band, whereas Cu(<small>II</small>) and Ni(<small>II</small>) exhibit minimal influence. Photophysical investigations reveal the {Ru<small>^II</small>Zn<small>₄</small>} compound as the only phosphorescent species, displaying an emission band extending into the near-infrared region. This emission originates from a triplet <small>³</small>MLCT state and features an exceptionally large Stokes shift, with a long lifetime of the excited-state of about 3.3 μs in powdered form at room temperature.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"62 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758069","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":"Coupling approaches for [Pt(1,10-phenanthroline)(1S,2S-diamminocyclohexane)dihydroxide]2+ using hydrazone and oxime ligation","authors":"Ashley Jurisinec, Jennette Sakoff, Jayne Gilbert, Christopher Gordon, Janice R Aldrich-Wright","doi":"10.1039/d5dt00303b","DOIUrl":"https://doi.org/10.1039/d5dt00303b","url":null,"abstract":"Established methods for conjugating biomolecules to non-conventional complexes such as [Pt(1,10-phenanthroline)(1S,2S-diamminocyclohexane)(OH)2]2+ (PtIVPhenSS) are limited in scope. To address this, we investigated amide, ester, and carbamate strategies, however we encountered significant issues with stability and thus yield. To overcome these shortcomings, we examined an imine linking strategy, using hydrazone and oxime ligation, which proved to be rapid and effective. Here we detail the synthesis of seven platinum(IV) complexes derived from PtIVPhenSS which demonstrate the suitability of an imine conjugation method as a potential linking strategy. Furthermore, we tested these complexes in broad panel of cancer cell lines, identifying that this strategy did not diminish the biological activity of the complex.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758500","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":"Defective carbonized wood membrane as a free-standing three-dimensional anode host for high-performance Zn-ion batteries","authors":"Jinyu Ma, Fang Wang, Zhengguo Zhang, Shixiong Min","doi":"10.1039/d5dt00073d","DOIUrl":"https://doi.org/10.1039/d5dt00073d","url":null,"abstract":"Three-dimensional (3D) porous carbons as the host matrix of Zn anode have been proven to be effective in suppressing Zn dendrite formation during the cycling of aqueous Zn-ion batteries (ZIBs), but the complex fabrication process and the lack of sufficient active sites for Zn nucleation still limit their practical applications. Herein, we develop a free-standing 3D carbon-based Zn anode (Zn/HDCW) by controllably electrochemically depositing Zn within highly defective, hierarchically porous carbonized wood carbon (HDCW) membrane obtained via the CO2 thermal etching of the carbonized wood (CW). The HDCW features not only numerous open aligned microchannels and excellent wettability for fast electrolyte transport but also abundant carbon defects for effectively binding with Zn²⁺, enabling uniform plating and stripping of Zn and thus greatly suppressing the formation of Zn dendrites. As a result, the Zn/HDCW-based symmetric cell exhibits long cycling stability nearing 2700 h at 1 mA cm-2 with low voltage hysteresis. Furthermore, the Zn/HDCW anode offers the corresponding aqueous Zn/HDCW-MnO2/HDCW full cell with remarkable rate capability and cycling stability, delivering an stable capacity of 170.8 mAh g-1 at 1 A g-1 after 600 cycles with a unit coulombic efficiency and an excellent capacity retention of 100%. This work provides a new insight into the development of 3D porous carbon-based Zn anodes for high-performance ZIBs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"36 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744745","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":"Gold bis(dithiolene) radical turning metallic under pressure: fusing pyrazine and dithiine rings on a dithiolene ligand†","authors":"Haia Kharraz, Pere Alemany, Enric Canadell, Thierry Roisnel, Hengbo Cui, Kee Hoon Kim, Marc Fourmigué, Dominique Lorcy","doi":"10.1039/d5dt00380f","DOIUrl":"https://doi.org/10.1039/d5dt00380f","url":null,"abstract":"Conducting molecular materials built on dithiolene complexes −as mixed-valence salts or single component materials− are most often based of planar structures which efficiently stack on top of each other. We report here an original dithiolene ligand, namely [1,4]dithiino[2,3-b]pyrazine-2,3-bis(thiolate) (hereafter noted as pzdtdt) which associates an electron-withdrawing pyrazine ring and a folded (by 40-50°) dithiine ring. While such strong distortions from planarity has hindered up to now the isolation of highly conducting materials from such dithiine-containing dithiolene complexes, we show here that the radical gold complex [Au(pzdtdt)2]•, obtained by electrocrystallization from the 1e− oxidation of [Ph4P][Au(pzdtdt)2], organizes in the solid-state into regular, non-dimerized chains, with a semi-conducting behavior at ambient pressure, turning metallic upon application of pressures above 4 GPa. The electronic structure of [Au(pzdtdt)2]• is discussed in terms of electron localization effects, through spin-polarized band-structure calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744740","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":"Molybdenum-modified ZnIn2S4 with Bifunctional Cocatalyst for Efficient Photocatalytic Overall Water Splitting under Simulated Sunlight","authors":"Yutong Chen, Rong Wu, Guoan Lin, Jianyong Yue, Dezheng Kong, Chen Zhang, Shunhang Wei, Xiaoxiang Xu","doi":"10.1039/d5dt00316d","DOIUrl":"https://doi.org/10.1039/d5dt00316d","url":null,"abstract":"Photocatalytic overall water splitting (POWS) was a promising technique for sustainable hydrogen provision that could potentially tackle the current energy and environmental challenges. As a visible-light-active photocatalyst, ZnIn2S4 was an ideal candidate for POWS yet was characterized with a low efficiency due to poor charge separation and improper surface reactions. Here, ZnIn2S4 was modified by doping Mo and depositing with bifunctional cocatalyst for efficient POWS under sunlight. Charge separation and photodeposition of Pt and CrOx was accelerated by Mo introduction to promote surface POWS reactions and suppress reverse reactions. Under simulated sunlight irradiation, the modified ZnIn2S4 achieved POWS with an apparent quantum efficiency (AQE) of 0.17% at 420  20 nm and a solar-to-hydrogen (STH) conversion efficiency of 0.016%. Theoretical calculations indicated that Mo dopants introduced spin-polarized states at both conduction band bottom and valence band top, being spin-forbidden for charge recombination. This study served as a useful guideline for the design and development of efficient photocataysts for sunlight-driven POWS.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744743","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":"Binding of potential antitumor Casiopeínas® with small proteins","authors":"Federico Pisanu, Giuseppe Sciortino, Feliu Maseras, Valeria UGONE, Daniele Sanna, Eugenio Garribba","doi":"10.1039/d5dt00228a","DOIUrl":"https://doi.org/10.1039/d5dt00228a","url":null,"abstract":"Casiopeínas® are a family of patented CuII anticancer compounds. Cas II-gly and Cas VII-gly are formed by 4,7-dimethyl-1,10-phenanthroline (Me<small>₂</small>phen) or 1,10-phenanthroline (phen), respectively, and the bidentate glycinato ligand (Gly), plus a nitrate anion acting as a counterion. In biological fluids, they can keep their identity or form mixed species and adducts with several bioligands, in particular with proteins. In this study, the binding of Cas II-gly, and Cas VII-gly for comparison, to small proteins like myoglobin (Mb), ubiquitin (Ub), and lysozyme (Lyz) was evaluated through combination of instrumental (ESI-MS and EPR) and computational (dockings) methods. Simulations of the peak signals in the ESI-MS spectra allow confirming the formation of the adducts. The results indicated that in all systems adducts with formula Protein–[Cu<small>^II</small>(Me<small>₂</small>phen)]<small>_n</small> with n = 1-3 are formed after the replacement of glycinato in the equatorial positions by side-chain donors. Dockings shows that the three proteins use different donor sets to bind the fragment Cu<small>^II</small>(Me<small>₂</small>phen)<small>²⁺</small>: (N<small>_His</small>, N<small>_His</small>) or (N<small>_His</small>, COO<small>^–</small><small>_Asp/Glu</small>) for Mb, N<small>_His68</small> or (COO<small>^–</small><small>_Glu/Asp</small>, COO<small>^–</small><small>_Glu/Asp</small>) for Ub, (COO<small>^–</small><small>_Glu/Asp</small>, CO) or only monodentate O donor for Lyz. The computational exploration of the protein structure reveals that more than one metal fragments can bind to the macromolecule. At the moment, it is not clear whether the formation of the adducts improves or worsens the action of Casiopeínas®. However, the obtained results suggest that, at the low copper concentrations found in the organism, the species Protein–[Cu<small>^II</small>(Me<small>₂</small>phen)]<em><small>_n</small></em> coexist with [Cu<small>^II</small>(Me<small>₂</small>phen)(Gly)]<small>⁺</small> and the fragment Cu<small>^II</small>(Me<small>₂</small>phen)<small>²⁺</small> which – in turn – could dissociate, at least partially, to Cu<small>²⁺</small> ion and free ligand Me<small>₂</small>phen. Therefore, a mixture of species could be responsible of the biological activity of Casiopeínas®.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744748","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":"σ-BH activation of NHC→BH3 fragments at dinuclear Cu complexes","authors":"Aurèle Camy, David Martins-Bessa, Laure Vendier, Israel Fernandez, Sébastien Bontemps","doi":"10.1039/d5dt00586h","DOIUrl":"https://doi.org/10.1039/d5dt00586h","url":null,"abstract":"We explored herein the coordination properties of bis(phosphine)NHC→BH3 ligand toward cationic and neutral Cu centres. The synthesis of three dinuclear Cu complexes featuring σ-BH interactions is reported. Noticeably, in each Cu complex, a BH moiety is bridging two Cu centres via two σ-BH interactions in a µ2-η1η1 BH coordination mode. NMR, IR, deuterium incorporation and X-Ray diffraction analyses, supported by DFT investigation enabled to finely measure the level of activation of the B-H bond depending on the coordination environment. The study shows gradual increase of activation whether the BH fragment is involved in none, one or two σ-BH interaction with Cu centres.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744741","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":"High-Yield Synthesis of Heavy Rare Earth(III) Anhydrous Solvates: Known, New, and Unexpected Products","authors":"Guilherme Augusto Augusto Barbosa, José Severiano Carneiro Neto, Bruno José Stoeberl, Sarita Wisbeck, Siddhartha Om Kumar Giese, Fabiano Yokaichiya, Daniel da Silva Costa, Andersson Barison, Ronny R Ribeiro, Leandro Piovan, David L. Hughes, Matteo Briganti, Giordano Poneti, Giovana Gioppo Nunes, Francielli Santana, Jaisa Fernandes Soares","doi":"10.1039/d5dt00254k","DOIUrl":"https://doi.org/10.1039/d5dt00254k","url":null,"abstract":"Ten anhydrous rare-earth (RE) chloride solvates were prepared by dehydration of RECl3·6H2O with triethylorthoformate (teof) in O-donor solvents as an accessible and general synthetic route. Reactions are quick, safe, mild, easily reproducible, and cost-effective. They run at room temperature or under reflux to give high-yield, pure crystalline products that are either new, as [Gd2Cl4(µ‒Cl)2(PriOH)6] (1) and [{GdCl(µ‒Cl)2(thf)2}∞] (2), or obtained for the first time from teof, such as [GdCl3(thf)4] (3), trans-[MCl2(thf)5]trans-[MCl4(thf)2], M = Gd (4), Dy (6), and Y (7), [YbCl3(thf)3] (8), and [MCl3(dme)2], M = Gd (5), Dy (9), and Er (10). Structural and spectroscopic characterization is presented for all products, and variable-temperature magnetic susceptibility data are discussed for the Dy3+ complexes 6 and 9. The latter behaves as a field-induced single-ion magnet for which theoretical (ab initio) and experimental data allowed a non-trivial assignment of overlapping high- (Orbach, Ueff 139 cm-1) and low-temperature (Raman, weff 46.8(2) cm-1) magnetic relaxation mechanisms (1kOe field). Besides the main products, unanticipated Lewis and redox reactivity led to serendipitous 11, [{Gd3Cl4(μ-Cl)4(μ-H3CCOO)(C3H8O2)(PriOH)4]∙PriOH}∞], and 12, [{(thf)2Cl2Gd(μ-Cl)2(μ3-O2)Gd(thf)3}2]·3thf, whose formation is discussed. The final RE3+ anhydrous complexes serve as valuable starting materials for numerous substitution reactions in coordination and organometallic chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"219 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744744","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}