The Royal Society of Chemistry最新文献

{"title":"Cobalt-nickel sandwich-type Dawson polyoxometalates as bifunctional OER/ORR electrocatalysts: the influence of metal arrangement.","authors":"Inês S Marques, Israël-Martyr Mbomekallé, Anne-Lucie Teillout, Pedro de Oliveira, António J S Fernandes, Diana M Fernandes","doi":"10.1039/d6dt00976j","DOIUrl":"10.1039/d6dt00976j","url":null,"abstract":"<p><p>The rising global need for sustainable energy has intensified research into environmentally friendly energy conversion technologies, such as fuel cells and electrochemical water splitting devices. The efficiency of these technologies is strongly influenced by the activity of electrocatalysts that enable the oxygen reduction (ORR) and evolution (OER) reactions. Noble metal-based electrocatalysts, including Pt, Pd, RuO₂ and IrO₂, are widely regarded as benchmark materials for these reactions due to their excellent electrocatalytic activity; nevertheless, their high cost, scarcity and limited long-term stability have prompted the development of alternatives. Polyoxometalates (POMs) have attracted considerable interest as a versatile class of materials, owing to their adjustable structures, redox properties and potential to serve as efficient and economically viable catalysts. In this research, we investigate two sandwich-type Dawson POM clusters containing cobalt and nickel ([CoNi₃(As₂W₁₅O₅₆)₂]^16- and [NiCo₃(As₂W₁₅O₅₆)₂]^16-) but with different spatial arrangements. The prepared electrocatalysts exhibited notable OER activity in alkaline media, achieving maximum current densities of 86.70 and 68.32 mA cm^-2 with corresponding overpotential values of 0.45 and 0.49 V <i>vs.</i> RHE, respectively. The electrocatalysts also demonstrated promising activity towards the ORR, with diffusion-limiting current densities of -2.98 and -2.33 mA cm^-2 and onset potentials of 0.82 and 0.78 V <i>vs.</i> RHE, respectively. This paper provides evidence suggestive of an influence of the metal centre position within the POM framework on the ORR/OER electrochemical performance and reinforces the potential of these hybrid materials as cost-effective and sustainable bifunctional electrocatalysts for next-generation energy devices.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14551-14562"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101070","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":"<i>N</i>,<i>N</i>'-Dialkyl-1,3-propanedialdiminate complexes of copper(I) and oxidation of β-dialdiminates by copper(II).","authors":"Claire E Schmit, Gregory S Girolami","doi":"10.1039/d6dt01303a","DOIUrl":"10.1039/d6dt01303a","url":null,"abstract":"<p><p>Three new copper(I) complexes derived from <i>N</i>,<i>N</i>'-dialkyl-β-dialdiminate anions (alkyl = iso-propyl or <i>tert</i>-butyl) are reported. Treatment of CuBr with Li[^<i>t</i>BuN(CH)₃N^<i>t</i>Bu] affords the tetrameric copper(I) compound Cu₄[^<i>t</i>BuN(CH)₃N^<i>t</i>Bu]₄. In this tetramer, the β-dialdiminate ligands adopt open-chain conformations that link the copper(I) centers into a boat-shaped 24-membered ring. Interestingly, the tetramer dissociates over several hours in solution into a dimer of stoichiometry Cu₂[^<i>t</i>BuN(CH)₃N^<i>t</i>Bu]₂. When copper(II) chloride is treated with Li[^<i>t</i>BuN(CH)₃N^<i>t</i>Bu], or copper(II) methoxide is treated with H[ⁱPrN(CH)₃NⁱPr], redox reactions take place in which the metal center is reduced to copper(I) and the β-dialdiminate anion or β-dialdimine is oxidized. Two copper(I) complexes containing oxidized β-dialdiminate groups have been isolated: in both complexes, the oxidized group has been dehydrogenated and oligomerized through C-C bond formation. All three compounds have been characterized by X-ray crystallography; selected NMR, IR, EA, and UV-Vis spectra are also reported.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14466-14474"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101046","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":"Hydrogen-bonded conjugated small molecules in organic electronics.","authors":"Miriam Más-Montoya, David Curiel","doi":"10.1039/d6cc05901e","DOIUrl":"https://doi.org/10.1039/d6cc05901e","url":null,"abstract":"<p><p>Organic semiconductors have become highly important for next-generation electronic devices. However, further research is needed to enhance their charge-transport properties and long-term stability. These challenges largely originate from their solid-state structure, as organic semiconductors are molecular solids whose organisation is governed by very weak non-covalent interactions. Accordingly, the weakness of intermolecular interactions increases the chances of having structural disorder and generating defects, which detrimentally affect the performance of organic semiconductors. Therefore, controlling molecular organisation is a key objective. Hydrogen bonding is particularly effective for promoting solid-state self-assembly and gaining certain control over molecular organisation. The strength of hydrogen bonds, their directionality, and the broad range of functional groups and structures that can act as hydrogen-bond donors and acceptors have encouraged their rational incorporation into the molecular design of organic semiconductors. This Feature Article presents a review of the structural approaches developed to enhance the performance of materials based on small molecules through the integration of hydrogen-bond donor and acceptor sites within the conjugated framework. It also discusses the implementation of these materials in different types of electronic devices.</p>","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How to enhance strain-release catalysis in a reaction through orbital alignment from metal catalysts?","authors":"Lopita Swain, Chinmaya Dihiria, Rajeev Ramanan","doi":"10.1039/d6dt01689h","DOIUrl":"10.1039/d6dt01689h","url":null,"abstract":"<p><p>The reaction rate of small ring cycloalkane transformations is primarily governed by strain release. The present study summarises how the interplay between substrate strain release and orbital orientations from the transition metal catalyst affects overall catalytic efficiency. Density functional theory (DFT) studies on a Rh(I) metal complex in a [5 + 1] cycloaddition reaction between vinylcyclopropane and CO are summarized. The free energy barriers for oxidative addition on singlet (7.7 kcal mol^-1) and triplet (25.6 kcal mol^-1) surfaces highlight how optimal orbital orientation in transition metal catalysts synergizes with strain release. The distortion-interaction energy analysis of singlet and triplet states confirmed the mechanism of synergy between strain release and orbital interaction. Distinct spin states tune the kinetics by modulating strain relief and electronic arrangements and effectively lower activation energies, enabling efficient [5 + 1] metal catalysed cycloadditions.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14349-14356"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148757031","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":"Photocatalytic hydrogen evolution by a molecular cobalt complex with polypyridyl-phenolate ligand in alkaline aqueous solutions.","authors":"Ping Wang, Nghia Le, Dade Walker, Axel E Galvez, John Daniel McCool, Bruno Donnadieu, Dmitry E Polyansky, Charles Edwin Webster, Xuan Zhao","doi":"10.1039/d6dt01631f","DOIUrl":"10.1039/d6dt01631f","url":null,"abstract":"<p><p>Solar-driven water-splitting represents a promising method of producing H₂ gas as a clean, renewable, and alternative fuel source. While proton reduction is thermodynamically more favorable in acidic pHs, hydrogen evolution reaction (HER) in neutral and basic media may be preferred for its coupling to the oxidation of water for overall water splitting. To further understand the electronic and steric effects that govern the structure-function relationships in catalytic HER, molecular Co complexes based on a pentadentate tetrapyridylamine ligand containing a phenol group were synthesized, characterized, and studied for photocatalytic HER. The octahedral Co^II-chloride complex with a dangling phenol group can be converted to a trigonal bipyramidal Co^II complex featuring a bound phenolate and a dangling pyridine moiety in aqueous solutions. The resulting Co complex with trigonal bipyramidal geometry shows considerable activity and improved stability for photocatalytic HER in purely basic aqueous solutions with turnover numbers ranging from 11 900-13 700 in pH 7-9 solutions. Results from DFT computations suggest either a modified electron transfer (E)-proton transfer (C)-electron transfer (E)-proton transfer (C) (mod-ECEC) or mod-CEEC pathway for HER depending on the protonation state of the ligand.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14541-14550"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101020","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":"Light-assisted hydrogen evolution at a Pt cathode using [Ru(bpy)₃]-intercalated layered MnO₂ anodes.","authors":"Hayato Sano, Ryota Sugawara, Rion Yamaguchi, Ryo Sasaki, Kazuaki Tomono","doi":"10.1039/d6dt01780k","DOIUrl":"10.1039/d6dt01780k","url":null,"abstract":"<p><p>Embedding photoactive coordination complexes within redox-active layered oxides offers a route to couple molecular excited-state chemistry with inorganic electrode reactions. Here, [Ru(bpy)₃]²⁺-intercalated layered MnO₂ was electrodeposited on a conductive bamboo-charcoal/carbon-nanotube composite and used as an anode for H₂ evolution at a Pt cathode. At +1.10 V <i>vs.</i> Ag/AgCl in 0.5 M Na₂SO₄, three independent experiments yielded 0.87 ± 0.15 mL H₂ after 3 h under 300 nm irradiation, 4.4 times the dark value (0.20 ± 0.05 mL), with a faradaic efficiency of 80.3 ± 14.4%. Although incident and estimated absorbed photon flux densities at 450 and 600 nm exceeded those at 300 nm by more than 400-fold, the 300 nm condition produced the largest H₂ evolution and total charge, excluding a simple light-intensity or whole-electrode-absorption explanation. Post-electrolysis spectroscopy, ICP-MS, and semiquantitative redox-potential analysis support a model in which photoexcitation of interlayer [Ru(bpy)₃]²⁺ contributes to Mn(III)/Mn(IV)-related redox cycling, while the elementary electron-transfer and ionic charge-compensation pathways remain unresolved. These findings show that interlayer coordination-complex design can couple molecular photoexcitation with redox-active layered oxide electrodes for light-assisted hydrogen generation.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14439-14457"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101027","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":"Emerging therapeutic strategies for triple-negative breast cancer using ruthenium, iridium, and rhenium complexes.","authors":"Rishav Das, Priyankar Paira","doi":"10.1039/d6dt01362g","DOIUrl":"10.1039/d6dt01362g","url":null,"abstract":"<p><p>Triple-negative breast cancer (TNBC) is an aggressive disease with limited treatment options due to the absence of ER, PR, and HER2 receptors. This review summarises the recent progress in the use of ruthenium, iridium, and rhenium complexes as alternative therapeutic agents for TNBC. These metal complexes are designed to respond to tumor-specific biomarkers or the tumor microenvironment, enabling selective uptake and enhanced anticancer activity. Through redox reactions and light activation, they generate reactive oxygen species, disrupt mitochondrial function, and induce cancer cell death. Overall, ruthenium, iridium, and rhenium complexes offer a multi-mechanistic and targeted approach that may help overcome resistance and improve future TNBC treatment strategies.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14304-14333"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148785450","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":"Aggregation-activated delayed and two-photon fluorescence in a charge-modulated pyridine-acridan luminophore.","authors":"Rasa Keruckiene, Kaspars Leduskrasts, Ho-Chia Tsai, Mariia Stanitska, Daiana Ospanova, Dmytro Volyniuk, Edgars Suna, Shi-Wei Chu, J V Grazulevicius","doi":"10.1039/d6cp02166b","DOIUrl":"https://doi.org/10.1039/d6cp02166b","url":null,"abstract":"<p><p>Molecular charge modulation offers a promising strategy for controlling the excited-state properties and aggregation behavior of organic luminophores. Nevertheless, the consequences of cationization strongly depend on the molecular structure. Herein, we investigate a twisted π-extended pyridine-dimethylacridan derivative (PyAcr) and its cationic pyridinium analogue (PyAcr+) to elucidate how neutral-to-cationic transformation affects their photophysical properties. Experimental characterization combined with theoretical calculations provides insight into the relationship between molecular structure, charge distribution, excited-state character, and emission behavior. PyAcr exhibits aggregation-induced delayed fluorescence (AIDF), accompanied by a moderate photoluminescence quantum yield of 45% and strong two-photon-excited fluorescence (TPEF) under near-infrared excitation. In contrast, conversion of PyAcr to PyAcr+ alters its aggregation behavior and results in substantially weakened emission, likely reflecting the combined effects of cation formation and the structural modification introduced upon quaternization. Both derivatives exhibit high thermal stability, with onset temperatures of thermal degradation above 360 °C, good electrochemical stability, and small singlet-triplet energy gaps of 0.07-0.13 eV. Overall, the results demonstrate that cationization alone does not necessarily enhance luminescence and that the interplay between molecular charge, electronic coupling, and aggregation is critical for controlling excited-state dynamics. These structure-property relationships provide useful guidelines for the rational design of environment-responsive luminophores, while PyAcr shows promise as a two-photon-excited probe for bioimaging.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222849","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":"Starting material syntheses for non-aqueous molecular uranium chemistry.","authors":"León Hillers, Rupesh, Lisa Vondung","doi":"10.1039/d6cs00827e","DOIUrl":"https://doi.org/10.1039/d6cs00827e","url":null,"abstract":"<p><p>Starting materials for non-aqueous uranium chemistry usually must be synthesised in-house, as they are rarely available commercially. Various routes to uranium precursors in oxidation states +III to +VI have been reported and developed further according to the availability of uranium compounds. This tutorial review discusses wet-chemical and selected solid-state routes to anhydrous uranium halide, amide and borohydride starting materials in oxidation states +III to +VI suitable for research laboratories. Oxidative, reductive, as well as halide interconversion routes are discussed to give a comprehensive overview on synthetically established routes and promising directions for future development.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel Pd-metalated porous organic phenanthroline-based polymer for heterogeneous cyanation of aryl halides.","authors":"Xuan Lai, Sanqi Liang, Wu Zhang, Jie Lin, Jiale Huang, Shunmin Ding, Shengjun Deng","doi":"10.1039/d6dt02206e","DOIUrl":"https://doi.org/10.1039/d6dt02206e","url":null,"abstract":"<p><p>The construction of porous organic phenanthroline-based polymers without functional groups is meaningful but also challenging, as they could offer a novel, single-site, stable platform for diverse catalytic applications. In this study, a unique strategy was devised to construct porous organic phenanthroline-based polymers (POP-Phen-X) without reactive/coordinating functional groups in the polymer skeleton. The polymers POP-Phen-X with high BET surface areas were synthesized using a solvent knitting Friedel-Crafts polymerization method. The well-defined and isolated phenanthroline sites of POP-Phen-X can serve as a platform for the immobilization of metal catalysts <i>via</i> coordination bonds. The post-synthetic metalation of POP-Phen-A with palladium(II) acetate afforded a selective heterogeneous Pd catalyst for the cyanation of aryl halides. The resulting Pd/POP-Phen-A exhibited effective catalytic performance towards the cyanation of aryl halides with a TON of 200 and good recyclability.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222902","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}