Xiao-Jun Wu, Hong-Yao Guo, Wei-Quan Lin, Yan Meng, Ji-Dong Leng
Three six-coordinate mononuclear lanthanide complexes of the formula [Ln{(O=PPh2)2CH2}2Cl2]Cl·THF based on the Kramers ions Dy3+ (1), Er3+ (2) and Yb3+ (3) have been synthesized and structurally characterized. Single-crystal X-ray diffraction reveals that these complexes adopt an octahedral geometry with cis-arranged chloride ligands and four oxygen atoms from two bidentate phosphine oxide ligands. The octahedral coordination sphere generates a crystal field environment conducive to field-induced slow magnetic relaxation for lanthanide ions with both oblate (Dy3+) and prolate (Er3+, Yb3+) electron density distributions. Under optimized direct-current fields, complexes 1Dy and 2Er show Orbach relaxation processes with effective energy barriers of 28.0(5) and 16.2(5) cm-1, respectively. In contrast, complex 3Yb exhibits more complex relaxation dynamics involving a combination of quantum tunnelling, direct, and Raman processes. Ab initio calculations demonstrate that complexes 1Dy and 2Er undergo magnetic relaxation through their first excited Kramers doublets, while the higher-lying first excited state in complex 3Yb (177 cm-1) prevents thermal relaxation via this pathway.
{"title":"Six-Coordinate Lanthanide Complexes Based on Bidentate Phosphine Oxide Ligands: Synthesis, Structure and Magnetic Properties","authors":"Xiao-Jun Wu, Hong-Yao Guo, Wei-Quan Lin, Yan Meng, Ji-Dong Leng","doi":"10.1039/d5dt00422e","DOIUrl":"https://doi.org/10.1039/d5dt00422e","url":null,"abstract":"Three six-coordinate mononuclear lanthanide complexes of the formula [Ln{(O=PPh2)2CH2}2Cl2]Cl·THF based on the Kramers ions Dy3+ (1), Er3+ (2) and Yb3+ (3) have been synthesized and structurally characterized. Single-crystal X-ray diffraction reveals that these complexes adopt an octahedral geometry with cis-arranged chloride ligands and four oxygen atoms from two bidentate phosphine oxide ligands. The octahedral coordination sphere generates a crystal field environment conducive to field-induced slow magnetic relaxation for lanthanide ions with both oblate (Dy3+) and prolate (Er3+, Yb3+) electron density distributions. Under optimized direct-current fields, complexes 1Dy and 2Er show Orbach relaxation processes with effective energy barriers of 28.0(5) and 16.2(5) cm-1, respectively. In contrast, complex 3Yb exhibits more complex relaxation dynamics involving a combination of quantum tunnelling, direct, and Raman processes. Ab initio calculations demonstrate that complexes 1Dy and 2Er undergo magnetic relaxation through their first excited Kramers doublets, while the higher-lying first excited state in complex 3Yb (177 cm-1) prevents thermal relaxation via this pathway.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"87 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837387","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 metallation, bonding, and electronic structure of redox active incomplete-cubane M3(μ3-Q)(μ2-Q)3 chalcogenide clusters with early actinides were studied using density functional theory and multireference methodologies. We confirmed that the incorporation of low-valent U(III) leads to its oxidation to U(IV) due to an intramolecular redox reaction with the molybdenum sulfide core. On the contrary, open questions remain with respect to the oxidation state of low-valent transuranic elements upon their coordination to the molybdenum sulfide core. Density functional theory calculations indicate that the transuranic center remains An(III), while complete active space calculations suggest an actinide oxidation analogous to the one observed in the uranium species. The predominantly electrostatic bonding between the actinides and the molybdenum sulfide cluster was confirmed using quantum theory of atoms in molecules. Our results on clusters with harder and softer chalcogenides are in agreement with a preferential soft-soft interaction between the actinide and its support.
{"title":"Electronic Structure of Molybdenum Chalcogenide Clusters as Supports for Low-Valent Actinides","authors":"Pere Miro, S. Genevieve Duggan","doi":"10.1039/d4dt02911a","DOIUrl":"https://doi.org/10.1039/d4dt02911a","url":null,"abstract":"The metallation, bonding, and electronic structure of redox active incomplete-cubane M<small><sub>3</sub></small>(μ<small><sub>3</sub></small>-Q)(μ<small><sub>2</sub></small>-Q)<small><sub>3</sub></small> chalcogenide clusters with early actinides were studied using density functional theory and multireference methodologies. We confirmed that the incorporation of low-valent U(III) leads to its oxidation to U(IV) due to an intramolecular redox reaction with the molybdenum sulfide core. On the contrary, open questions remain with respect to the oxidation state of low-valent transuranic elements upon their coordination to the molybdenum sulfide core. Density functional theory calculations indicate that the transuranic center remains An(III), while complete active space calculations suggest an actinide oxidation analogous to the one observed in the uranium species. The predominantly electrostatic bonding between the actinides and the molybdenum sulfide cluster was confirmed using quantum theory of atoms in molecules. Our results on clusters with harder and softer chalcogenides are in agreement with a preferential soft-soft interaction between the actinide and its support.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837455","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}
Marco Filippo Gatto, Sara Sangtarash, David Jago, R. Tom Abram, Eleanor Barrett, Amit Sil, George Koutsantonis, Simon Higgins, Craig Robertson, Richard J. Nichols, Hatef Sadeghi, Andrea Vezzoli
It is becoming increasingly evident that transition metal complexes impart desirable qualities in single-molecule electronics, and testing metallic centres in combination with appropriate ligands is salient to building the next generation of single-molecule devices. Metal-phosphine complexes have been the subject of very few studies, despite their extensive use in other areas of chemistry. In this contribution, we fabricated and studied robust single-molecule junctions using linear bischelated ligand-metal-ligand complexes of the type [M(PNP)2]PF6 (M = Cu(I), Ag(I) or Au(I); PNP = bis(diphenylphosphino)aniline functionalised with methylthio contact groups). The robustness of the devices was evinced by surface-enhanced Raman spectroscopy (SERS) and scanning-tunnelling microscopy break junction (STM-BJ) methods, and the conductance of the devices was found to be independent of the central transition metal. Quantum transport calculations show consistent HOMO-LUMO gaps between the studied complexes in the transmission plots, supporting the experimental findings. This study shows that bischelation is a viable approach to the fabrication of stable and robust metal-phosphine devices.
{"title":"Metal Ion Independent Conductance Through Bis-chelated Metal Complex Molecular Wires based on a Bis(diphenylphosphino)aniline Derivative","authors":"Marco Filippo Gatto, Sara Sangtarash, David Jago, R. Tom Abram, Eleanor Barrett, Amit Sil, George Koutsantonis, Simon Higgins, Craig Robertson, Richard J. Nichols, Hatef Sadeghi, Andrea Vezzoli","doi":"10.1039/d5dt00292c","DOIUrl":"https://doi.org/10.1039/d5dt00292c","url":null,"abstract":"It is becoming increasingly evident that transition metal complexes impart desirable qualities in single-molecule electronics, and testing metallic centres in combination with appropriate ligands is salient to building the next generation of single-molecule devices. Metal-phosphine complexes have been the subject of very few studies, despite their extensive use in other areas of chemistry. In this contribution, we fabricated and studied robust single-molecule junctions using linear bischelated ligand-metal-ligand complexes of the type [M(PNP)2]PF6 (M = Cu(I), Ag(I) or Au(I); PNP = bis(diphenylphosphino)aniline functionalised with methylthio contact groups). The robustness of the devices was evinced by surface-enhanced Raman spectroscopy (SERS) and scanning-tunnelling microscopy break junction (STM-BJ) methods, and the conductance of the devices was found to be independent of the central transition metal. Quantum transport calculations show consistent HOMO-LUMO gaps between the studied complexes in the transmission plots, supporting the experimental findings. This study shows that bischelation is a viable approach to the fabrication of stable and robust metal-phosphine devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841534","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}
Ali Tufani, Nina Popov, Janez Kovac, Stanislav Čampelj, Andraž Mavrič, Tomas Landovsky, Martin Cigl, Petra Vaňkátová, Martin Loula, Vladimira Novotna, Matic Poberžnik, Gabriela Herrero-Saboy, Layla Martin-Samos, Alenka Mertelj, Darja Lisjak
Ferrofluids composed of permanently magnetic nanoplatelets of barium hexaferrite (BHF NPLs) represent a remarkable class of materials that can form a ferromagnetic liquid state at sufficiently high concentrations. To date, the surfactant dodecylbenzenesulfonic acid (DBSA) has demonstrated an excellent colloidal stability of the BHF NPLs in alcohols. However, a key limitation of DBSA is its labile adsorption onto the NPLs, meaning that the surface coverage by surfactant molecules is highly sensitive to various factors. In this study, we demonstrate that polar ligands based on phosphonic acids and phosphonate esters offer a viable alternative to DBSA, providing enhanced robustness and colloidal stability in low-polar solvents. Phosphonic ligands with the different electron-withdrawing groups and alkyl chain lengths of the terminal chain and linker were synthesized. Their attachment to the surface of the BHF NPLs was studied for various conditions and followed by a combination of spectroscopic techniques, thermogravimetry, and electrokinetic measurements. The results confirmed the theoretically predicted surface condensation of the ligands onto the BHF NPLs surfaces at 120 °C in 1-hexanol, whereas at lower temperatures or in more polar solvents the ligands were mostly physisorbed. The NPL hybrids with chemisorbed ligands having surface densities of at least 0.4 molecules/nm2 formed stable ferrofluids in 1-hexanol. Due to the relatively low polarity of 1-hexanol, the ligands remain protonated and the ferrofluids have negligible electric conductivity and are suitable for the development of novel magneto-optic sensors that can operate under an electric field.
{"title":"Nonconductive ferrofluids from permanently magnetic nanoplatelets hybridized with polar phosphonic ligands","authors":"Ali Tufani, Nina Popov, Janez Kovac, Stanislav Čampelj, Andraž Mavrič, Tomas Landovsky, Martin Cigl, Petra Vaňkátová, Martin Loula, Vladimira Novotna, Matic Poberžnik, Gabriela Herrero-Saboy, Layla Martin-Samos, Alenka Mertelj, Darja Lisjak","doi":"10.1039/d5dt00281h","DOIUrl":"https://doi.org/10.1039/d5dt00281h","url":null,"abstract":"Ferrofluids composed of permanently magnetic nanoplatelets of barium hexaferrite (BHF NPLs) represent a remarkable class of materials that can form a ferromagnetic liquid state at sufficiently high concentrations. To date, the surfactant dodecylbenzenesulfonic acid (DBSA) has demonstrated an excellent colloidal stability of the BHF NPLs in alcohols. However, a key limitation of DBSA is its labile adsorption onto the NPLs, meaning that the surface coverage by surfactant molecules is highly sensitive to various factors. In this study, we demonstrate that polar ligands based on phosphonic acids and phosphonate esters offer a viable alternative to DBSA, providing enhanced robustness and colloidal stability in low-polar solvents. Phosphonic ligands with the different electron-withdrawing groups and alkyl chain lengths of the terminal chain and linker were synthesized. Their attachment to the surface of the BHF NPLs was studied for various conditions and followed by a combination of spectroscopic techniques, thermogravimetry, and electrokinetic measurements. The results confirmed the theoretically predicted surface condensation of the ligands onto the BHF NPLs surfaces at 120 °C in 1-hexanol, whereas at lower temperatures or in more polar solvents the ligands were mostly physisorbed. The NPL hybrids with chemisorbed ligands having surface densities of at least 0.4 molecules/nm<small><sup>2</sup></small> formed stable ferrofluids in 1-hexanol. Due to the relatively low polarity of 1-hexanol, the ligands remain protonated and the ferrofluids have negligible electric conductivity and are suitable for the development of novel magneto-optic sensors that can operate under an electric field.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837388","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}
Only merury(II) and silver(I) ions specifically bind to natural and naturally modified base pairs in duplex DNA to form metal-mediated base pairs. We found novel specific binding of copper ion to naturally modified base pairs involving 5-fluorouracil(FdU) in duplex DNA to form C–Cu–FdU and FdU–Cu–C.
{"title":"Novel specific binding of copper ions to naturally modified base pairs involving 5-fluorouracil in duplex DNA","authors":"Hidetaka Torigoe, Kei Hirabayashi, Saki Adachi, Jiro Kondo","doi":"10.1039/d5dt00619h","DOIUrl":"https://doi.org/10.1039/d5dt00619h","url":null,"abstract":"Only merury(II) and silver(I) ions specifically bind to natural and naturally modified base pairs in duplex DNA to form metal-mediated base pairs. We found novel specific binding of copper ion to naturally modified base pairs involving 5-fluorouracil(FdU) in duplex DNA to form C–Cu–FdU and FdU–Cu–C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832301","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}
Roman A Khalaniya, Valeriy Verchenko, Andrey V. Mironov, Alexander N. Samarin, Alexey Bogach, Aleksandr Kulchu, Alexey O. Polevik, Wei Zheng, Evgeny V. Dikarev, Raivo Stern, Andrei V Shevelkov
Fe32+δGe35−xSix was synthesized using solid-state and chemical vapor transport reactions both in powder and single crystalline forms. Single crystal and high-resolution powder X-ray diffraction experiments revealed Fe32+δGe35−xSix to be a third member of the Fe32+δGe35−xEx (E = p-element) family of ternary compounds alongside Fe32+δGe33As2 and Fe32+δGe35−xPx. Fe32+δGe35−xSix features a two-dimensional intergrowth structure of two parent structure types: MgFe6Ge6 and Co2Al5. Similarly to the other members, the stabilisation of the intergrowth structure in Fe32+δGe35−xSix occurs as a result of the p-element substitution in the MgFe6Ge6-type block. The intergrowth breaks the kagome net of MgFe6Ge6 into individual hexagrams, while providing additional layers of geometrically frustrated atomic arrangements. Magnetic measurements showed antiferromagnetic ordering at TN ~ 150–160 K and spin reorientation below 80–90 K owing to the competition between magnetic interactions in the frustrated magnetic lattice of Fe32+δGe35−xSix.
{"title":"Spin reorientation and magnetic frustration in Fe32+δGe35−xSix with a kagome lattice broken by crystallographic intergrowth","authors":"Roman A Khalaniya, Valeriy Verchenko, Andrey V. Mironov, Alexander N. Samarin, Alexey Bogach, Aleksandr Kulchu, Alexey O. Polevik, Wei Zheng, Evgeny V. Dikarev, Raivo Stern, Andrei V Shevelkov","doi":"10.1039/d5dt00654f","DOIUrl":"https://doi.org/10.1039/d5dt00654f","url":null,"abstract":"Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> was synthesized using solid-state and chemical vapor transport reactions both in powder and single crystalline forms. Single crystal and high-resolution powder X-ray diffraction experiments revealed Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> to be a third member of the Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>E<small><sub>x</sub></small> (E = <em>p</em>-element) family of ternary compounds alongside Fe<small><sub>32+δ</sub></small>Ge<small><sub>33</sub></small>As<small><sub>2</sub></small> and Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>P<small><sub>x</sub></small>. Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> features a two-dimensional intergrowth structure of two parent structure types: MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small> and Co<small><sub>2</sub></small>Al<small><sub>5</sub></small>. Similarly to the other members, the stabilisation of the intergrowth structure in Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> occurs as a result of the p-element substitution in the MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small>-type block. The intergrowth breaks the kagome net of MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small> into individual hexagrams, while providing additional layers of geometrically frustrated atomic arrangements. Magnetic measurements showed antiferromagnetic ordering at <em>T</em><small><sub>N</sub></small> ~ 150–160 K and spin reorientation below 80–90 K owing to the competition between magnetic interactions in the frustrated magnetic lattice of Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"41 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832296","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}
Yoel Garrosa-Miró, Laura Muñoz-Moreno, Gerardino D'Errico, Matilde Tancredi, M. Jose Carmena, M. Francesca Ottaviani, Paula Ortega, Javier de la Mata
Ruthenium or copper complexes have emerged as some of the most promising alternatives for the treatment of many types of cancer. They have enhanced activity, greater selectivity and reduced side effects compared to their predecessors, cisplatin and its analogues. On the other hand, polyamine metabolism is often deregulated in cancer, leading to increased intracellular concentrations of polyamines that promote cell proliferation, differentiation, and tumorigenesis. In the present work, we report the synthesis and characterization of a family of mono- and binuclear Ru(II) and Cu(II) complexes functionalized with polyamine ligands derived from norspermine. The computer-aided analysis of the electron paramagnetic resonance (EPR) spectra provided magnetic and dynamic parameters, which helped to identify prevalent Cu–N2 coordination in a partially distorted square planar geometry of the Cu(II) complexes and the flexibility of the complexes in solution, slowed down by both the complex size and the hydrophobic interactions between chains. In vitro studies focused on advanced prostate cancer have demonstrated that these new metal complexes present a high level of cytotoxicity against PC3 cells. Furthermore, these metallic compounds exhibit the ability to inhibit cell adhesion and migration while reducing intracellular reactive oxygen species levels, which are key factors of metastasis.
{"title":"Ruthenium(II) and copper(II) polyamine complexes as promising antitumor agents: synthesis, characterization, and biological evaluation","authors":"Yoel Garrosa-Miró, Laura Muñoz-Moreno, Gerardino D'Errico, Matilde Tancredi, M. Jose Carmena, M. Francesca Ottaviani, Paula Ortega, Javier de la Mata","doi":"10.1039/d4dt03377a","DOIUrl":"https://doi.org/10.1039/d4dt03377a","url":null,"abstract":"Ruthenium or copper complexes have emerged as some of the most promising alternatives for the treatment of many types of cancer. They have enhanced activity, greater selectivity and reduced side effects compared to their predecessors, cisplatin and its analogues. On the other hand, polyamine metabolism is often deregulated in cancer, leading to increased intracellular concentrations of polyamines that promote cell proliferation, differentiation, and tumorigenesis. In the present work, we report the synthesis and characterization of a family of mono- and binuclear Ru(<small>II</small>) and Cu(<small>II</small>) complexes functionalized with polyamine ligands derived from norspermine. The computer-aided analysis of the electron paramagnetic resonance (EPR) spectra provided magnetic and dynamic parameters, which helped to identify prevalent Cu–N2 coordination in a partially distorted square planar geometry of the Cu(<small>II</small>) complexes and the flexibility of the complexes in solution, slowed down by both the complex size and the hydrophobic interactions between chains. <em>In vitro</em> studies focused on advanced prostate cancer have demonstrated that these new metal complexes present a high level of cytotoxicity against PC3 cells. Furthermore, these metallic compounds exhibit the ability to inhibit cell adhesion and migration while reducing intracellular reactive oxygen species levels, which are key factors of metastasis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"108 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832242","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}
Pd-based catalysts have emerged as one unique class of the promising catalysts capable of selectively producing formate near the equilibrium potential during CO2 electroreduction, but still suffering from CO-poisoning at high overpotentials. Achieving an excellent overall performance, including a high formate selectivity, a wide potential window, and a high anti-CO-poisoning ability, remains a significant challenge. Herein, we report the surfactant-templated synthesis of ultrathin, two-dimensional (2D) binary PdAg alloy mesoporous nanosheets enriched with nanogaps among interlinked branches with regulated atomic stoichiometry for highly efficient CO2 reduction to formate. These advanced structural features enable the catalysts to expose abundant active sites, whereas a proper Ag concentration within alloy effectively tailors the electronic structure of Pd through the electron transfer from Ag to Pd. The synergy effect resulting from the structural and electronic perspectives contributes to greatly promoting electrocatalytic CO2 reduction to formate. As a result, the optimized Pd4Ag1 nanosheets display a maximal formate faradic efficiency of 99.4% at −0.1 V versus reversible hydrogen electrode and exhibit a wide potential window of 400 mV for high formate selectivity (>90 %) toward CO2 reduction. Moreover, the detailed electrochemical analyses collectively evidence that Pd4Ag1 nanosheets exhibit attenuated CO binding and CO poisoning. This work highlights a feasible avenue for elaborate designing and constructing efficient formate-targeted catalysts.
{"title":"Ultrathin, 2D PdAg alloy mesoporous nanosheets enriched with nanogaps promote electrocatalytic CO2 reduction to formate","authors":"Shangqing Sun, Miaomiao Liu, Yalan Mao, Fang Liu, Xinyuan Xu, Yuan Li, Ximei Lv, Shulin Zhao, Xiaojing Liu, Yuping Wu, Yuhui Chen","doi":"10.1039/d5dt00436e","DOIUrl":"https://doi.org/10.1039/d5dt00436e","url":null,"abstract":"Pd-based catalysts have emerged as one unique class of the promising catalysts capable of selectively producing formate near the equilibrium potential during CO2 electroreduction, but still suffering from CO-poisoning at high overpotentials. Achieving an excellent overall performance, including a high formate selectivity, a wide potential window, and a high anti-CO-poisoning ability, remains a significant challenge. Herein, we report the surfactant-templated synthesis of ultrathin, two-dimensional (2D) binary PdAg alloy mesoporous nanosheets enriched with nanogaps among interlinked branches with regulated atomic stoichiometry for highly efficient CO2 reduction to formate. These advanced structural features enable the catalysts to expose abundant active sites, whereas a proper Ag concentration within alloy effectively tailors the electronic structure of Pd through the electron transfer from Ag to Pd. The synergy effect resulting from the structural and electronic perspectives contributes to greatly promoting electrocatalytic CO2 reduction to formate. As a result, the optimized Pd4Ag1 nanosheets display a maximal formate faradic efficiency of 99.4% at −0.1 V versus reversible hydrogen electrode and exhibit a wide potential window of 400 mV for high formate selectivity (>90 %) toward CO2 reduction. Moreover, the detailed electrochemical analyses collectively evidence that Pd4Ag1 nanosheets exhibit attenuated CO binding and CO poisoning. This work highlights a feasible avenue for elaborate designing and constructing efficient formate-targeted catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832294","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}
Metal oxide nanoparticles are commonly used as electron transport layers (ETLs) in quantum dot light emitting diodes (QLEDs) because of their wide band gap, high electron mobility, and appropriate conduction and valence band positions. Currently, ZnO nanoparticles are the most successfully electron transportation material in high-performance QLEDs. However, the positive aging effect is widely observed for ZnO-based QLEDs since the amphiprotic ZnO nanoparticles are not stable under the acidic, basic, and moisture conditions, which limits their applications. In this study, highly dispersible and alcohol-soluble TiO₂ nanoparticles are synthesized by using a non-hydrolytic sol-gel method, followed by a dimethyl sulfoxide post-treatment. The use of colloidal TiO₂ nanoparticles as an ETL yields optimal QLED, with a maximum external quantum efficiency of 12.03%, a highest luminance of 103,420 cd/m², and a current efficiency of 18.06 cd/A. These results reveal that TiO₂ nanoparticles hold great potential as ETL in the future QLEDs.
{"title":"Synthesis of Highly DispersibleTiO2 Nanoparticles and Their Application in Quantum Dot Light Emitting Diodes","authors":"Botao Hu, Mengxin Liu, Xinan Shi, Daocheng Pan","doi":"10.1039/d5dt00410a","DOIUrl":"https://doi.org/10.1039/d5dt00410a","url":null,"abstract":"Metal oxide nanoparticles are commonly used as electron transport layers (ETLs) in quantum dot light emitting diodes (QLEDs) because of their wide band gap, high electron mobility, and appropriate conduction and valence band positions. Currently, ZnO nanoparticles are the most successfully electron transportation material in high-performance QLEDs. However, the positive aging effect is widely observed for ZnO-based QLEDs since the amphiprotic ZnO nanoparticles are not stable under the acidic, basic, and moisture conditions, which limits their applications. In this study, highly dispersible and alcohol-soluble TiO₂ nanoparticles are synthesized by using a non-hydrolytic sol-gel method, followed by a dimethyl sulfoxide post-treatment. The use of colloidal TiO₂ nanoparticles as an ETL yields optimal QLED, with a maximum external quantum efficiency of 12.03%, a highest luminance of 103,420 cd/m², and a current efficiency of 18.06 cd/A. These results reveal that TiO₂ nanoparticles hold great potential as ETL in the future QLEDs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832297","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 series of rare earth iodate sulfate UV compounds, Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu), have been successfully synthesized by hydrothermal method at 200 °C. These isostructural compounds all crystallize in the noncentrosymmetric space group P212121 (No. 19) and feature a neutral three-dimensional Ln(IO3)(SO4) framework which is composed of 2D cationic Ln[SO4]+ layers bridged by anionic [IO3]- trigonal pyramids through sharing corner oxygen atoms. Under 1064 nm laser irradiation, Y(IO3)(SO4)·3H2O exhibits a second-harmonic generation (SHG) with efficiency of 0.7 × KDP@1064 nm. Furthermore, Y(IO3)(SO4)·3H2O has a moderate birefringence (0.118@532 nm) and large band gap (4.60 eV) and may be a potential UV nonlinear optical material. For Eu(IO3)(SO4)·3H2O, it emits intense photoluminescence peaks at 594 nm and 617 nm when excited under 393 nm near-ultraviolet light, showing promising applications as red phosphors of white-LED. The current study elucidates that the incorporation of highly anisotropic lone-paired (IO3)- units into highly isotropic (SO4)2- sulfate groups can achieve balanced SHG response, optical band gap and birefringence, facilitating the development of novel iodate sulfate crystals for UV nonlinear optical applications.
{"title":"Achieving balanced UV SHG response, optical band gap and birefringence in rare earth compounds Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu)","authors":"Shihua Ma, Lei Geng, Baozhu Zhu, Chang Yu Meng","doi":"10.1039/d5dt00613a","DOIUrl":"https://doi.org/10.1039/d5dt00613a","url":null,"abstract":"A series of rare earth iodate sulfate UV compounds, Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu), have been successfully synthesized by hydrothermal method at 200 °C. These isostructural compounds all crystallize in the noncentrosymmetric space group P212121 (No. 19) and feature a neutral three-dimensional Ln(IO3)(SO4) framework which is composed of 2D cationic Ln[SO4]+ layers bridged by anionic [IO3]- trigonal pyramids through sharing corner oxygen atoms. Under 1064 nm laser irradiation, Y(IO3)(SO4)·3H2O exhibits a second-harmonic generation (SHG) with efficiency of 0.7 × KDP@1064 nm. Furthermore, Y(IO3)(SO4)·3H2O has a moderate birefringence (0.118@532 nm) and large band gap (4.60 eV) and may be a potential UV nonlinear optical material. For Eu(IO3)(SO4)·3H2O, it emits intense photoluminescence peaks at 594 nm and 617 nm when excited under 393 nm near-ultraviolet light, showing promising applications as red phosphors of white-LED. The current study elucidates that the incorporation of highly anisotropic lone-paired (IO3)- units into highly isotropic (SO4)2- sulfate groups can achieve balanced SHG response, optical band gap and birefringence, facilitating the development of novel iodate sulfate crystals for UV nonlinear optical applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"60 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832295","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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