Dalton Transactions最新文献

{"title":"Catalytic evaluation of MOF-808 with metallic centers of Zr(IV), Hf (IV) and Ce(IV) in the acetalization of benzaldehyde with methanol","authors":"Yazmín Arellano, Cesar Pazo-Carballo, Vanesa Roa, Yoan Hidalgo-Rosa, Ximena Zárate, Jaime Llanos, Nestor Escalona, Eduardo Schott","doi":"10.1039/d4dt01959h","DOIUrl":"https://doi.org/10.1039/d4dt01959h","url":null,"abstract":"In the context of climate change, it is of utmost importance to replace the use of fossil fuels as raw material in areas of industrial interest, for example, in the production of chemical inputs. In this context, a viable option is biomass, since by subjecting it to chemical processes such as pyrolysis, it is possible to obtain platform molecules that are the basis for the generation of value-added chemical products. Acetals are molecules obtained from biomass derivatives, which have various applications in cosmetic chemistry, in the pharmaceutical industry as intermediates or final compounds, food additives, among others. Different catalysts have been used in the acetalization reaction, including MOFs, which have the advantage of being porous materials with high surface area values. The large surface area translates into a greater number of catalytically active sites available for the reaction. Among the MOFs that have been used for this purpose is MOF-808, which is characterized by having a lower number of ligands attached to its metal cluster, therefore, it has a greater exposure to the metals that make up its structure. In this context, the work carried out studied the catalytic performance of MOF-808 when its Zr(IV) metal centers are replaced by Hf(IV) and Ce(IV) atoms in the acetalization reaction of benzaldehyde with methanol. The MOFs obtained by solvothermal synthesis were characterized by powder X-ray diffraction, N2 adsorption and desorption, FT-IR spectroscopy, acid-base potentiometric titration, XPS and thermogravimetric analysis. The results of the catalysis indicate that the MOF with the best performance was MOF-808-Ce, which achieved conversions greater than 80% in a period of ten minutes. MOF-808-Ce exhibits a higher number of defects and therefore a higher availability of catalytic sites for the reaction to occur, which explains the better performance. Finally, the performance of MOF-808 in the acetalization of benzaldehyde with methanol was also supported by density functional theory (DFT) calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171014","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":"NaZr2(PO4)3 – a cubic langbeinite-type sodium-ion solid conductor","authors":"Sergey N. Marshenya, Alexey G. Scherbakov, Artem D. Dembitskiy, Alexander A. Golubnichiy, Ivan A. Trussov, Aleksandra A. Savina, Sergey M. Kazakov, Dmitry A. Aksyonov, Evgeny V. Antipov, Stanislav S. Fedotov","doi":"10.1039/d4dt02288b","DOIUrl":"https://doi.org/10.1039/d4dt02288b","url":null,"abstract":"The synthesis of langbeinite-type phosphates with small cations such as Li<small>⁺</small> or Na<small>⁺</small> <em>via</em> a high-temperature solid-state reaction is a challenging task due to the predominant formation of a related NaSICON-type phase. This work reports on the synthesis route, crystal structure, thermal behavior, and Na-conductive properties of the langbeinite-type NaZr<small>₂</small>(PO<small>₄</small>)<small>₃</small> prepared by a mechanochemically activated ion-exchange reaction between hydrothermally prepared NH<small>₄</small>Zr<small>₂</small>(PO<small>₄</small>)<small>₃</small> and NaNO<small>₃</small>. The crystal structure of NaZr<small>₂</small>(PO<small>₄</small>)<small>₃</small> is refined based on X-ray diffraction data and validated by Fourier-transformed infrared spectroscopy. NaZr<small>₂</small>(PO<small>₄</small>)<small>₃</small> is found to be stable up to 730 °C, undergoing a transformation into the NaSICON phase with further heating. Notably, in the 25–500 °C range, the material shows negative thermal expansion. The Na<small>⁺</small> conductivity within the range of 50–225 °C amounts to 1.7 × 10<small>⁻⁸</small> S cm<small>⁻¹</small> at 50 °C and 1 × 10<small>⁻⁶</small> S cm<small>⁻¹</small> at 225 °C with an activation energy of 0.44 eV, accompanied by a sufficiently low (∼10<small>⁻¹²</small> S cm<small>⁻¹</small>) electronic conductivity. The bandgap of 4.44 eV and the electrochemical stability window covering the 1.39–4.18 V <em>vs.</em> Na/Na<small>⁺</small> range are calculated using density functional theory. The obtained results open up opportunities for designing langbeinite-structured phosphates as potential solid electrolytes for Na-ion batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166374","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":"Observation of Haldane Magnetism in Organically Templated Vanadium Phosphate (enH2)0.5VPO4OH","authors":"Aleksandr Sh. Samarin, Stanislav S. Fedotov, Hyun-Joo Koo, Mike Whangbo, Andrei Gippius, Sergei Zhurenko, Alexey V. Tkachev, Larisa Victorovna Shvanskaya, Alexander Vasiliev","doi":"10.1039/d4dt01675k","DOIUrl":"https://doi.org/10.1039/d4dt01675k","url":null,"abstract":"We prepared an organically templated magnet, (<em>en</em>H<small>₂</small>)<small>_0.5</small>VPO<small>₄</small>OH (<em>en</em>H<small>₂</small> = diprotonated ethylenediamine), hydrothermally and characterized its crystal structure by powder X-ray diffraction and Fourier-transform infrared spectroscopy, and its physical properties by magnetization, specific heat and nuclear magnetic resonance measurements and density functional theory calculations. (<em>en</em>H<small>₂</small>)<small>_0.5</small>VPO<small>₄</small>OH consists of uniform chains of V<small>³⁺</small>(d<small>²</small>, <em>S</em> = 1) ions and exhibits Haldane magnetism with spin gap Δ = 59.3 K from the magnetic susceptibility χ(<em>T</em>) at µ<small>₀</small><em>H</em> = 0.1 T, which is reduced to 48.4 K at µ<small>₀</small><em>H</em> = 9 T according to the <small>³¹</small>P shift. The NMR data evidence the formation of a spin-glass state of unpaired <em>S</em> = 1/2 spins at <em>T</em><small>_S-G</small> ≈ 3 K and indicate that the Haldane <em>S</em> = 1 spin chain segments are much longer in the organically templated magnet (<em>en</em>H<small>₂</small>)<small>_0.5</small>VPO<small>₄</small>OH than in the ammonium counterpart NH<small>₄</small>VPO<small>₄</small>OH. The single-ion anisotropy <em>D</em> and the interchain exchange <em>J</em>' in (<em>en</em>H<small>₂</small>)<small>_0.5</small>VPO<small>₄</small>OH and NH<small>₄</small>VPO<small>₄</small>OH were estimated in density functional calculations to find them very weak compared to the intrachain exchange <em>J</em>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166378","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":"A Dawson-type {P4W24} modified by phenylphosphonic acid with excellent proton conductivity†","authors":"Jiayu Liu, Wenjing Lei, Shihao Zhang, Huafeng Li, Siyu Liu, Pengtao Ma, Jingping Wang, Jingyang Niu","doi":"10.1039/d4dt01775g","DOIUrl":"https://doi.org/10.1039/d4dt01775g","url":null,"abstract":"A case of organic-inorganic hybridized phosphotungstate modified by aromatic organophosphonic acid, K4Na4H11[KCo2(H2O)10P4W24O92{(PhPO)2]·48H2O (1), was successfully synthesized in conventional aqueous solution. The prominent structural feature is that the total structure of the [KP4W24O92{(PhPO)2]]23− resembles an V-shaped structure, which was stabilized by two [Co(H2O)5]2+ ions. Further, it can be connected into three-dimensional mesh structure by K+ ions. Surprisingly, 1 possesses a remarkably high proton conductivity of 1.59 × 10−2 S cm−1 at 95% RH, 318 K, probably due to its structure contains large amount of lattice water, coordination water and counter cations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166375","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":"Yttrium-based metal-organic frameworks built on hexanuclear clusters","authors":"Shenfang Li, Tao Shen, Manglai Gao, Hao Wang","doi":"10.1039/d4dt01658k","DOIUrl":"https://doi.org/10.1039/d4dt01658k","url":null,"abstract":"Yttrium-based metal-organic frameworks built on hexanuclear clusters (Y6-MOFs) represent an important subgroup of MOFs that are assembled from Y6 clusters and diverse organic linkers, featuring a variety of topologies. Due to the robust Y-O bonds and high connectivity of hexanuclear SBUs, Y6-MOFs are generally thermally stable and resistant to water. Additionally, their pore structures are highly tunable through the practice of reticular chemistry strategy, resulting in excellent performance in gas adsorption and separation related applications. Y6-MOFs are structurally analogous to Zr6-MOFs; however, the existence of charge-balancing cations in Y6-MOFs serves as an additional pore structure regulator, enhancing their tailorability with respect to pore shape and dimensions. In this Frontier article, we summarize the main advances in the design and synthesis of Y6-MOFs, with a particular focus on the precise engineering of their pore structure for gas separations. Future directions of research efforts in this field are also discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166377","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":"Quantum Tunnelling Effect in the Cis-Trans Isomerization of Uranyl Tetra Hydroxide","authors":"Yeshayahu Ben-Eliyahu, Sebastian Kozuch","doi":"10.1039/d4dt02071e","DOIUrl":"https://doi.org/10.1039/d4dt02071e","url":null,"abstract":"The role of Quantum Tunnelling (QT) in the proton transfer kinetics of the Uranyl Tetra Hydroxide (UTH, [UO<small>₂</small>(OH)<small>₄</small>]<small>^2-</small>) cis to trans isomerization was computationally studied under three possible reaction pathways. The first involved a direct proton transfer between the hydroxide ligand to the oxo atom. In the other two one or two water molecules were added to the second sphere. The first H<small>₂</small>O, bound by hydrogen bonds to the ligands, acts as a bridge enabling a proton shuttling, a concerted hoping of a proton from the hydroxide to the oxo atom similar to the Grotthuss mechanism. In the third pathway the second water molecule does not participate in the H-transfer chain, but works as an anchor for the first water, limiting its movement and therefore enhancing the QT. Since experimentally the reaction occurs in water, the first two pathways (no water or one H<small>₂</small>O) serve only as models of the gas phase behaviour, while the third pathway will always be thermodynamically and kinetically preferred. The effects were investigated in gas phase as well as in a continuum aqueous model, including the H/D Kinetic Isotope Effect (KIE). The results indicate that at very low temperatures QT is the only mechanism that permits the reaction kinetics, consistent with the large computed KIE. At higher temperatures, thermally-activated tunnelling competes with the classical crossing over the potential barrier.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166376","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":"A New Family of Heterometallic [Cu6M4] (M = Gd, Tb, Dy and Y) Clusters Derived from the Combined use of Selected Pyridyl Poly-alcohol Ligands","authors":"Antonis Anastassiades, Dimitris I. Alexandropoulos, Christian D. Buch, Stergios Piligkos, Anastasios Tasiopoulos","doi":"10.1039/d4dt02054e","DOIUrl":"https://doi.org/10.1039/d4dt02054e","url":null,"abstract":"The combined use of 2-(2-pyridyl)-1,3-propane-diol (pypdH2) and 2-hydroxymethyl-2-(2-pyridyl)-1,3-propane-diol (pyptH3) in Cu2+/4f chemistry has afforded a new family of isostructural [Cu6M4(pypt)4(pypdH)4(NO3)8] [M = Gd (1), Tb (2), Dy (3), and Y (4)] complexes. These compounds are based on an unprecedented three-layered symmetric [Cu6M4(μ-ΟR)16]8+ structural core, formed from the connection of the metal ions by bridging alkoxide arms of the organic ligands. Direct current magnetic susceptibility studies for complexes 1 - 3 revealed the presence of dominant ferromagnetic exchange interactions, suggesting the existence of large spin ground state values. Alternating current magnetic studies indicate the presence of slow-magnetic relaxation in 1 - 3.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166178","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":"Electronic structure, colour-tunable emission and energy transfer in Li3Ba2Y3(WO4)8:Bi3+,Eu3+ phosphors for white light-emitting diodes†","authors":"Junqiang Gu, Feiyan Xie, HuaJiang Yu, Shengqian Wang, Chaochao Tao, Houfa Mao, Shuo Wang, Hualan Xu and Shengliang Zhong","doi":"10.1039/D4DT02121E","DOIUrl":"10.1039/D4DT02121E","url":null,"abstract":"<p >Solid-state phosphor-converted white light-emitting diodes (pc-WLEDs) are the leading trend of the lighting industry in the 21st century. To pursue high quality WLED lighting, the development of highly efficient phosphors with tunable luminescence has become a hot research topic. Herein, we reported for the first time on Bi<small>³⁺</small>/Eu<small>³⁺</small>-doped Li<small>₃</small>Ba<small>₂</small>Y<small>₃</small>(WO<small>₄</small>)<small>₈</small> phosphors that exhibited tunable emission and high energy transfer efficiency of 89.90% from Bi<small>³⁺</small> to Eu<small>³⁺</small>. The phase purity, microstructure, electronic structure and photoluminescence properties of these phosphors were studied in detail. Bi<small>³⁺</small> and Eu<small>³⁺</small> were effectively doped in Li<small>₃</small>Ba<small>₂</small>Y<small>₃</small>(WO<small>₄</small>)<small>₈</small> with an optical bandgap of 3.81 eV. The band structure and density of states were quantitatively evaluated by density functional theory simulation. At an excitation wavelength of 342 nm, the Bi<small>³⁺</small>-doped phosphor achieved yellow-green emission. By alloying Eu<small>³⁺</small> into Li<small>₃</small>Ba<small>₂</small>Y<small>₃</small>(WO<small>₄</small>)<small>₈</small>:Bi<small>³⁺</small>, the luminescence gradually turned red due to the energy transfer from Bi<small>³⁺</small> to Eu<small>³⁺</small>. Moreover, the activation energy of the prepared phosphor was 0.1897 eV, demonstrating excellent thermal stability. Eventually, by combining Li<small>₃</small>Ba<small>₂</small>Y<small>₃</small>(WO<small>₄</small>)<small>₈</small>:4%Bi<small>³⁺</small>,4%Eu<small>³⁺</small> and a blue-emitting BAM:Eu<small>²⁺</small> phosphor with a 365 nm ultraviolet chip, a WLED device with a high colour rendering index (<em>R</em><small>_a</small>) of 78.7, chromaticity coordinates of (0.3401, 0.3131) and correlated colour temperature of 5080 K was successfully achieved. This work provided new insights into the design and development of color-tunable phosphors for white LEDs.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165870","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":"Octahedral molybdenum iodide clusters with pyrazole or pyrazolate ligands","authors":"Ksenia S. Kozlova, Alexey S. Berezin, Natalia Kuratieva, Michael A. Shestopalov, Anton A. Ivanov","doi":"10.1039/d4dt01831a","DOIUrl":"https://doi.org/10.1039/d4dt01831a","url":null,"abstract":"Due to the combination of useful physicochemical properties (luminescence, X-ray contrast, etc.), octahedral molybdenum halide cluster complexes [Mo<small>₆</small>X<small>₈</small>L<small>₆</small>]<small>ⁿ</small> have been the subject of active investigation during the last decades. The most common methods for synthesizing new compounds with organic ligands involve the use of silver salts of organic acids or the substitution of terminal methylate ligands. However, these methods often necessitate the use of special conditions, such as an inert atmosphere, absolute solvents, and silver salts, which can be costly. In contrast, aqua-hydroxo complexes formed by hydrolysis of many complexes are considered final unreactive products, despite the tendency for them to form. This work proposes a simple and affordable method for the preparation of hexaaqua and hexahydroxo iodide clusters of molybdenum from [Mo<small>₆</small>I<small>₁₄</small>]<small>^2–</small> in a single step. Furthermore, the possibility of using such compounds as starting complexes for the synthesis of clusters with organic ligands such as pyrazole is discussed. The paper presents synthetic approaches, detailed characterization both in solid and in solution, and a study of the reactivity and luminescent properties of the obtained compounds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166380","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":"Keplerate Polyoxometalate Compounds: A Multifunctional Nano-Platform for Advanced Materials","authors":"Ken Wang, Tsukasa Iwano, Sayaka Uchida","doi":"10.1039/d4dt02114b","DOIUrl":"https://doi.org/10.1039/d4dt02114b","url":null,"abstract":"Polyoxometalates (POMs) are robust, discrete, and structurally well-defined metal-oxide cluster anions that have stimulated research in broad fields of sciences. Keplerates, as porous giant POMs, serve as a multifunctional nano-platform exhibiting fascinating chemical properties stemming from the porous molecular structure, substantial interior space, delocalization of d-electrons over the large molecular surface, etc. Consequently, Keplerates have attracted significant attention from scientists in the fields of chemistry, physics, biology, and material sciences. This work reviews recent research progress on Keplerates as nanocontainers, catalysts, or battery materials. Furthermore, current challenges and potential future research directions are discussed, providing a reference for the development and effective application of Keplerates and Kepelerate-based materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166379","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}