Dalton Trans [JOURNAL]
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200 papers
Cation-templated synthesis of a FeCo cyanometallate cluster.
Chen ZY, Yang J, Ma J … +2 more , Cheng Y, Zhang YZ
Dalton Trans · 2026 Jul · PMID 42397182 · Publisher ↗
Despite significant progress in the synthesis of cyanometallate complexes with well-defined structures and tunable magnetic properties, the construction of high-nuclearity cyanometallate clusters remains a major syntheti...
Despite significant progress in the synthesis of cyanometallate complexes with well-defined structures and tunable magnetic properties, the construction of high-nuclearity cyanometallate clusters remains a major synthetic challenge. Herein, we report the successful preparation of a high-nuclearity Fe/Co cyanometallate cage, , using a hierarchical, cation-templated assembly strategy. This approach involves the incorporation of a preorganized Co subcluster into a "super-square" framework through cyanide bridging, directed by a tetraethylammonium (NEt) cation acting as a structure-directing template with an approximately square geometry. Within the resulting discrete cluster, the cobalt centers exhibit diverse coordination environments, including NO, NO, and NCl, giving rise to an exceptional degree of structural complexity. Magnetic studies reveal dominant antiferromagnetic interactions, with no evidence of long-range magnetic ordering down to 2 K. This work highlights the potential of cation-templated synthesis as an effective strategy for constructing complex cyanometallate clusters with tunable magnetic and functional properties.
High-field multinuclear MAS NMR and synchrotron XANES reveal the influence of strontium salt chemistry on geopolymer nanostructure.
O'Donoghue KT, Geddes DA, Wilkinson TJ … +5 more , Stennett MC, Kim B, Iuga D, Hayes M, Walkley B
Dalton Trans · 2026 Jul · PMID 42397003 · Full text
This study investigates the influence of strontium (Sr) salt chemistry (Sr(OH)·8HO, SrCO, Sr(NO), and SrSO) on the nanostructural evolution of potassium silicate-activated geopolymers. High-field multinuclear (Al, Si, K,...
This study investigates the influence of strontium (Sr) salt chemistry (Sr(OH)·8HO, SrCO, Sr(NO), and SrSO) on the nanostructural evolution of potassium silicate-activated geopolymers. High-field multinuclear (Al, Si, K, and Sr) MAS NMR, synchrotron XANES, EPMA, XRD, and FTIR showed that while the primary binding phase in all samples is a disordered, highly cross-linked K-A-S-H gel, the Sr immobilisation mechanism is governed by salt solubility. Soluble nitrate and hydroxide salts release Sr ions that are chemically incorporated into the K-A-S-H gel framework in brewsterite-type pseudo-zeolitic environments. In contrast, insoluble carbonate and sulfate salts act primarily as physical fillers, and are encapsulated as discrete particles within the geopolymer matrix, though sulfate additionally reacts to form secondary crystalline kalistrontite (KSr(SO)). Sr adsorption on metakaolin surfaces is found to inhibit early-stage Al dissolution, resulting in a Si-rich K-A-S-H gel that transitions to an Al-rich K-A-S-H gel over 28 days. These results provide new insight into the mechanisms of immobilisation of Sr in geopolymers, and highlight their potential as wasteforms for long-term management of Sr radioactive waste.
Carbonyl insertion into metal-boron based clusters: pathway to a rhodathiacarborane.
Luaces S, Bould J, Lahoz FJ … +1 more , Macías R
Dalton Trans · 2026 Jul · PMID 42396972 · Publisher ↗
The reaction of the ten-vertex hydridorhodathiaborane [2,2,2-(H)(PPh)--2,1-RhSBH] (1) with excess of carbon monoxide at room temperature yields a novel eleven-vertex rhodathiacarborane [1,1-(CO)(PPh)-3-(OH)--1,2,3-RhSCBH...
The reaction of the ten-vertex hydridorhodathiaborane [2,2,2-(H)(PPh)--2,1-RhSBH] (1) with excess of carbon monoxide at room temperature yields a novel eleven-vertex rhodathiacarborane [1,1-(CO)(PPh)-3-(OH)--1,2,3-RhSCBH] (4). The formation of 4 involves the substitution of a PPh ligand by CO at the rhodium centre and the subsequent insertion of a second CO molecule into the polyhedral cage to form a hydroxy-functionalized carbon vertex (C-OH). In addition to 4, the reaction affords the CO-ligated ten-vertex adducts [6,6-(CO)(PPh)-9-(PPh)--6,5-RhSBH] (5a) and [9,9-(CO)(PPh)-8-(PPh)--9,6-RhSBH] (5b). While a mixture of 5a and 5b can also be synthesized from the PPh-adduct [6,6-(PPh)-9-(PPh)--6,5-RhSBH] (2), compound 2 does not yield 4 upon treatment with CO. This suggests that the transformation of CO into a C-OH vertex is mediated by a specific CO-Rh/PPh intermediate. Similarly, the reaction of the 2-methyl-pyridine adduct, [6,6-(PPh)-9-(2-Mepy)--6,5-RhSBH] (3) with CO selectively yields the CO-ligated isomer [6,6-(CO)(PPh)-9-(2-Mepy)--6,5-RhSBH] (6). All the compounds were characterized by multielement NMR spectroscopy and mass spectrometry, with 4, 5a and 6 further analysed by single-crystal X-ray diffraction. Variable temperature NMR and DFT calculations for 4 reveal a fluxional process characterized by the rotation of the {Rh(CO)(PPh)} unit relative to the thiacarborane cage. These findings underscore the versatility of rhodathiaborane platforms for the activation and incorporation of small molecules metal-polyhedron cooperation.
Simulation of displacement damage in CsPbBr induced by neutron irradiation based on the Monte Carlo method.
Wang X, Yu Q, Yi Z … +3 more , Liu L, Zhang Y, Liu Z
Dalton Trans · 2026 Jul · PMID 42396857 · Publisher ↗
Cesium lead bromide (CsPbBr) is a fully inorganic halide perovskite material known for its excellent optoelectronic properties, offering significant advantages for applications in aerospace and nuclear fields. To evaluat...
Cesium lead bromide (CsPbBr) is a fully inorganic halide perovskite material known for its excellent optoelectronic properties, offering significant advantages for applications in aerospace and nuclear fields. To evaluate its radiation hardness under neutron exposure, the transport process of 1-14 MeV neutrons in CsPbBr was simulated using the Geant4 Monte Carlo toolkit. This study focuses on the primary damage characteristics, systematically analyzing the primary knock-on atom (PKA) spectrum and non-ionizing energy loss (NIEL). The simulation results indicate that most PKAs are distributed in the low-energy range. As the incident neutron energy increases, PKA types become more diverse, introducing transmutation products such as Se, Xe, As, and Hg. Furthermore, a distinct anomaly is observed at lower neutron energies (∼3 MeV), where the displacement of Pb atoms exhibits a localized peak directly attributed to its prominent (n, n) elastic scattering resonance, although the overall macroscopic damage remains heavily dominated by the Br sublattice. Crucially, the calculated NIEL, number of displaced atoms (), and displacements per atom (dpa) exhibit a non-monotonic dependence on incident neutron energy, initially increasing and then decreasing beyond ∼10 MeV. This trend is primarily driven by the transition from elastic to inelastic scattering dominance, coupled with increased ionizing energy partitioning at higher PKA energies. This paper provides fundamental data on the primary damage state of CsPbBr, establishing an essential source term basis for subsequent multiscale simulations of defect evolution.
Photocatalysis-tribocatalysis synergy in oxygen vacancy-rich ZnSnO: mechanism and enhanced all-day performance.
Wu D, Liu Y, Sheng Y … +6 more , Yang Z, Hu C, Qiu P, Liu J, Fu C, Wang J
Dalton Trans · 2026 Jul · PMID 42396827 · Publisher ↗
Oxygen vacancy engineering has emerged as a cutting-edge strategy to remarkably boost the catalytic performance of photocatalysis and tribocatalysis for efficient pollutant degradation. Nevertheless, feasible strategies...
Oxygen vacancy engineering has emerged as a cutting-edge strategy to remarkably boost the catalytic performance of photocatalysis and tribocatalysis for efficient pollutant degradation. Nevertheless, feasible strategies for regulating oxygen vacancies to fabricate bifunctional catalysts are still severely limited. Herein, we demonstrate that oxygen vacancies in ZnSnO generate defect-mediated pathways that intrinsically synergize photocatalytic and tribocatalytic mechanisms. HSE06 theoretical calculations reveal that the induced defect states simultaneously narrow the bandgap and reduce the work function, which not only act as sustainable electron donors for tribocatalysis but also generate an interfacial electric field to prominently accelerate photogenerated charge separation. The introduction of tribocatalysis significantly boosts the first-order photocatalytic rate constant from 0.245 h to 0.326 h, which is 1.33-fold higher than that of single photocatalysis. Furthermore, the bifunctional ZnSnO catalyst circumvents the intrinsic light dependence of conventional photocatalysis and achieves a pollutant degradation efficiency of 92% under alternating light conditions, exhibiting outstanding all-weather catalytic performance. This work constructs a multi-energy-driven, illumination-independent catalytic paradigm based on defect-mediated photocatalysis-tribocatalysis synergy.
Two-dimensional Co/Ni coordination polymers: structure-activity relationship and bifunctional performance for electrocatalysis and energy storage.
Sun PP, Li YH, Xing JJ … +1 more , Liu HY
Dalton Trans · 2026 Jul · PMID 42396635 · Publisher ↗
Two two-dimensional layered porous coordination polymers (Co-MOCP and Ni-MOCP) were synthesized a hydrothermal route. Both materials possess high crystallinity, uniform elemental distribution and excellent structural st...
Two two-dimensional layered porous coordination polymers (Co-MOCP and Ni-MOCP) were synthesized a hydrothermal route. Both materials possess high crystallinity, uniform elemental distribution and excellent structural stability in an alkaline environment. Electrochemical measurements show that Co-MOCP has better bifunctional electrocatalytic performance for the HER and OER, with Tafel slopes of 132.7 mV dec and 64.96 mV dec, and a double-layer capacitance of 1.849 mF cm. For supercapacitors, Co-MOCP delivers a specific capacitance of 602 F g at 1 A g and a capacity retention of 80.1% after 10 000 cycles, outperforming Ni-MOCP in all electrochemical indicators. Frontier molecular orbital calculations indicate that Co-MOCP has a narrow HOMO-LUMO band gap of 0.1463 eV and delocalized orbitals, which facilitate electron transfer and redox reactions. In contrast, Ni-MOCP has a band gap of 0.91 eV with localized orbitals, resulting in restricted charge transport and weak redox activity. This study elucidates the regulatory effect of metal centers on material properties and provides guidance for designing low-cost high-performance multifunctional electrode materials.
Ligand-field modulation, Jahn-Teller distortion and redox behavior in Cu(II) Schiff base complexes.
Vatagude SD, Horitani M, Gurubasavaraj PM
Dalton Trans · 2026 Jul · PMID 42394591 · Publisher ↗
Cu(II) Schiff base complexes constitute a structurally versatile class of coordination compounds in which ligand architecture exerts decisive control over geometry, ligand-field stabilization and redox accessibility. Thi...
Cu(II) Schiff base complexes constitute a structurally versatile class of coordination compounds in which ligand architecture exerts decisive control over geometry, ligand-field stabilization and redox accessibility. This feature article organizes known ligand-field and redox trends for Cu(II) Schiff base complexes into a comparative structure-electronic-reactivity heuristic based on donor topology, chelate rigidity, and π-conjugation. Rigid, planar donor environments impose strong equatorial ligand fields that reinforce a ground-state electronic configuration with predominant d SOMO character in d Cu(II) systems, while reducing geometric reorganization during electron transfer and enhancing metal-ligand covalency. In contrast, flexible multidentate frameworks introduce geometric dispersion and increased structural fluxionality, broadening electronic distributions and attenuating redox predictability. Reported frontier orbital separations and electrochemical parameters are evaluated as qualitative descriptors within the limitations of heterogeneous computational and experimental methodologies. By abstracting recurring geometric and electronic motifs into qualitative structure-reactivity relationships, this feature article proposes a ligand-field-guided heuristic for rational scaffold selection in redox-active Cu(II) coordination systems.
Postsynthetic modification of N-heterocyclic diazoolefins backbone metallation.
Kooij B, Lange SN, Fadaei-Tirani F … +2 more , Scopelliti R, Severin K
Dalton Trans · 2026 Jul · PMID 42390383 · Full text
Diazoolefins can be functionalized by postsynthetic modification backbone metallation. Reactions with electrophiles allow the regioselective introduction of silyl, phosphino, stannyl, borate, and alcoholate groups. The...
Diazoolefins can be functionalized by postsynthetic modification backbone metallation. Reactions with electrophiles allow the regioselective introduction of silyl, phosphino, stannyl, borate, and alcoholate groups. The methodology was also used for the synthesis of a silyl-bridged bis-diazoolefin.
Lanthanide-based MOFs derived from 1,3-bis(diphenylphosphoryl)-2-oxapropane.
Slobodskaia SS, Tsebrikova GS, Ilyukhin AB … +5 more , Ivanova IS, Pyatova EN, Grinchenko AE, Baulin VE, Tsivadze AY
Dalton Trans · 2026 Jul · PMID 42390356 · Publisher ↗
Neutral phosphoryl podands with flexible ethylene glycol chains and diphenylphosphorylmethyl end groups are known for their complexation properties towards various cations. In this work, 2D and 3D lanthanide metal-organi...
Neutral phosphoryl podands with flexible ethylene glycol chains and diphenylphosphorylmethyl end groups are known for their complexation properties towards various cations. In this work, 2D and 3D lanthanide metal-organic frameworks (MOFs) with 1,3-bis(diphenylphosphoryl)-2-oxapropane (L) were synthesized. They were characterized by X-ray methods, IR spectroscopy and thermogravimetric analysis (TGA). The effect of the position of the metal ion Ln in the lanthanide series on the structure of the synthesized MOFs was studied. Among the light lanthanides with ligand L, Ce and Pr form only 2D MOFs, while Sm, Eu, and Nd can form both 2D and 3D MOFs in various solvent systems. Correlations between the structure of the obtained MOFs and the synthesis conditions were established. The metal ions of heavy lanthanides with a smaller radius are characterized by the formation of only 3D MOFs. The adsorption ability for CO of the synthesized compounds was studied. The specific surface areas of the Tm and Pr MOFs were 120 m g and 13 m g, respectively.
Improving the anticancer efficacy of azole-platinum(II) complexes through a Pluronic® micelle formulation strategy.
Kaszuba A, Sitkowski J, Muzioł T … +7 more , Tafelska-Kaczmarek A, Pokrzywka K, Kaźmierski Ł, Gurgul I, Maj M, Dąbrowski JM, Łakomska I
Dalton Trans · 2026 Jul · PMID 42390168 · Publisher ↗
Four new azole-platinum(II) complexes with the general formulas -[PtCl(L1)] (1), -[PtCl(L2)] (2), -[PtCl(L1)(DMSO)] (3), and -[PtCl(L2)(DMSO)] (4), where L1 is 1-(benzofuran-2-yl)-2-(1-1,2,4-triazol-1-yl)ethenone, L2 is...
Four new azole-platinum(II) complexes with the general formulas -[PtCl(L1)] (1), -[PtCl(L2)] (2), -[PtCl(L1)(DMSO)] (3), and -[PtCl(L2)(DMSO)] (4), where L1 is 1-(benzofuran-2-yl)-2-(1-1,2,4-triazol-1-yl)ethenone, L2 is (benzofuran-2-yl)-2-(1-imidazol-1-yl)ethenone, and DMSO is dimethyl sulfoxide, were synthesized and fully characterized. The compositions of the coordination spheres were established using spectroscopic methods (H, C, N, Pt NMR; IR; X-ray). Complexes (1) and (2) adopted geometries, featuring two triazole ligands L1 in (1) or two imidazole ligands L2 in (2), each coordinated through the nitrogen donor atom N4″, along with two chloride ions. In contrast, complexes (3) and (4) exhibited configurations and contained one azole ligand (L1 or L2), each coordinated a nitrogen donor N4″ atom, an S-donor DMSO molecule, and two chloride ions. All complexes displayed moderate lipophilicity (logP = 0.92-1.12) and markedly reduced reactivity toward glutathione compared with cisplatin, reflecting the steric shielding provided by the azole ligands. Despite these favorable physicochemical features, only complex (1) demonstrated notable intrinsic cytotoxicity. It showed activity against a lung cancer cell line (A549) and four bladder cancer cell lines (T24, HT1376, 5637, and HB-CLS-1), with IC values ranging from 5.00 to 8.50 µM. Comparable toxicity was observed toward normal SV-HUC-1 urothelial cells (IC = 8.54 µM). Notably, complex (1) induced only minor alterations in the cell-cycle profile, suggesting a mechanism of action distinct from those of classical DNA-targeting platinum drugs. To improve its therapeutic performance, complex (1) was encapsulated in polymeric micelles formed by PEO-PPO-PEO triblock copolymers. This nanoformulation resulted in a striking increase in anticancer activity, yielding submicromolar IC values (0.13-0.94 µM). The corresponding toxicity toward normal SV-HUC-1 cells ranged from IC = 0.17 to 0.75 µM. The substantial increase in potency suggests that micellar delivery enhances intracellular accumulation while protecting the complex from premature deactivation. These results suggest that triazole-based platinum(II) complexes, particularly when combined with polymeric nanocarriers, may represent a promising system for further investigation in the development of platinum-based chemotherapeutic drugs.
Isolation of a trigonal bipyramidal Mn(II) diradical complex with an intermediate spin state ( = 3/2).
Das S, Schwarz B, Mondal KC
Dalton Trans · 2026 Jul · PMID 42389937 · Publisher ↗
Isolation of Mn(II) complexes featuring an intermediate spin state ( = 3/2) is quite rare. Previous studies have only speculated on the existence of such species in systems such as paddle-wheel-type tris(cyclopentadienyl...
Isolation of Mn(II) complexes featuring an intermediate spin state ( = 3/2) is quite rare. Previous studies have only speculated on the existence of such species in systems such as paddle-wheel-type tris(cyclopentadienyl)manganese(II) and tris(allyl)manganese(II) anions, which are proposed to exhibit mixed = 3/2 and = 5/2 states based on theoretical investigations. Herein, we report on the isolation and structural characterisation of an unprecedented Mn(II)-bis(dithiolene-radical) complex (1), in which the Mn(II) centre adopts a distorted trigonal bipyramidal coordination geometry and possesses an intermediate spin state ( = 3/2). Magnetic susceptibility and EPR studies revealed that the Mn(II) centre, coordinated by an S donor set, is antiferromagnetically coupled to two unpaired electrons on the chelating ligands. Complex 1 has been further characterised by XPS, IR, UV-Vis, and Raman spectroscopy. The redox property of 1 was investigated using cyclic voltammetry measurements. 1- was generated in THF solution the reduction of 1 with KC.
Novel ruthenium(II) complexes bearing polypyridyl and 1,2,4-oxadiazole ligands: from synthesis to and anticancer evaluation.
Marretta L, Valcanover D, Buono MP … +7 more , Pirker C, Amata S, Keppler BK, Palumbo Piccionello A, Terenzi A, Berger W, Barone G
Dalton Trans · 2026 Jul · PMID 42389930 · Publisher ↗
We report on the synthesis and characterization of four novel Ru(II) polypyridyl complexes incorporating bipyridine or phenanthroline ancillary ligands. Substituted 1,2,4-oxadiazoles are introduced here for the first tim...
We report on the synthesis and characterization of four novel Ru(II) polypyridyl complexes incorporating bipyridine or phenanthroline ancillary ligands. Substituted 1,2,4-oxadiazoles are introduced here for the first time as chelating ligands for Ru(II), and the structure of a representative complex unequivocally established by single-crystal X-ray diffraction. The antiproliferative activity of the metal complexes in human colorectal (HCT116 and oxaliplatin- and BOLD-100-resistant derivatives) and ovarian (A2780 and A2780cis) cancer cell lines was evaluated. The presence of phenanthroline ancillary ligands induced the highest cytotoxicity, with platinum-resistant cells displaying enhanced sensitivity compared to parental lines. Cellular uptake of the metal complexes was quantified by ICP-MS. Finally, tests were conducted in BALB/c mice using the most promising compound, to evaluate its toxicity profile and its ability to inhibit CT-26 tumor growth. Interestingly, both duplex and G-quadruplex DNA can be excluded as potential molecular targets, as assessed by FRET-melting assays, UV-Vis spectroscopy, and circular dichroism.
Halogen substitution of aromatic cations for phase transition control and high-efficiency luminescence in 0D manganese-based hybrid perovskites.
Yu K, Wu Y, Yang Y … +1 more , Ye Q
Dalton Trans · 2026 Jul · PMID 42389880 · Publisher ↗
Zero-dimensional (0D) organic-inorganic hybrid manganese halides are emerging as attractive materials for optoelectronic applications, owing to their structural versatility, low toxicity, and excellent luminescence prope...
Zero-dimensional (0D) organic-inorganic hybrid manganese halides are emerging as attractive materials for optoelectronic applications, owing to their structural versatility, low toxicity, and excellent luminescence properties. Nevertheless, achieving simultaneous control over phase transition behavior and photoluminescence quantum yield (PLQY) through molecular-level design remains challenging. In this work, two 0D manganese-based hybrid compounds with distinct halogen substitution patterns, (2,5-DFBTP)MnBr (1) and (2-Cl-5-FBTP)MnBr (2) (2,5-DFBTP = (2,5-difluorobenzyl)trimethylphosphonium; 2-Cl-5-FBTP = (2-chloro-5-fluorobenzyl)trimethylphosphonium), are successfully synthesized and systematically investigated. By rationally tuning spatial distribution of halogen substituents on the organic cation, concurrent modulation of the phase transition energy barrier and (Photoluminescence Quantum Yield) PLQY is realized. Compound 1 exhibits a reversible phase transition at 428.5 K, whereas compound 2 shows no detectable phase transition across the measured temperature range. At the same time, the PLQY is markedly enhanced from 58.35% to 93.33%, accompanied by a pronounced narrowing of the emission bandwidth and improved color purity. Detailed structural analysis reveals that the variation in halogen substitution not only alters the phase transition energy barrier but also optimizes luminescence performance by regulating the Mn-Mn distance, introducing C-Cl⋯Br halogen bonding interactions to reinforce lattice rigidity. This work demonstrates the effectiveness of halogen synergy engineering in tailoring the structure-phase transition-luminescence relationship, and provides a viable strategy for the development of high-performance manganese-based emitters and multifunctional optoelectronic materials.
Stepwise C-H bond activations and assembly of binuclear Ln species coordinated by a hexaanionic -η:η-dibenzopentalene-bridged bis(carbazolyl) framework.
Zakaria H, Félix G, Lyubov DM … +7 more , Kallio M, Vieru V, Vologzhanina AV, Aysin RR, Guari Y, Larionova J, Trifonov AA
Dalton Trans · 2026 Jul · PMID 42385240 · Publisher ↗
New binuclear rare-Earth complexes [(μ-η:η;κ:κ-N,C-)Ln(THF)] (Ln = Y (1Y), Tb (1Tb), Dy (1Dy), and Er (1Er)) containing a hexaanionic dibenzopentalene-bridged bis(carbazolyl) framework were obtained spontaneous self-ass...
New binuclear rare-Earth complexes [(μ-η:η;κ:κ-N,C-)Ln(THF)] (Ln = Y (1Y), Tb (1Tb), Dy (1Dy), and Er (1Er)) containing a hexaanionic dibenzopentalene-bridged bis(carbazolyl) framework were obtained spontaneous self-assembly in the reactions of Ln(CHSiMe)(THF) with an equimolar amount of 3,6-di--butyl-1,8-bis(phenylethynyl)-9-carbazole. Two Ln ions are μ--η:η-coordinated with the dianionic dibenzopentalene fragment resulting from a series of successive intramolecular -CH activations in the phenyl rings of the ethynyl substituents followed by intermolecular dimerization involving Ln-C bond addition to a CC triple bond. Magnetic investigations show that 1Dy behaves as a genuine single-molecule magnet (SMM) with relaxation dynamics described by a multicomponent phenomenological relaxation model yielding an effective energy barrier of 689 cm. In contrast, 1Tb and 1Er exhibit only field-induced slow magnetic relaxation at low temperature. calculations reveal a substantially larger crystal-field splitting and stronger axial anisotropy for Dy than for the Er analogue. Weak antiferromagnetic interactions between the lanthanide centers were identified with = -0.23 cm for 1Dy, -0.06 cm for 1Tb, and -0.28 cm for 1Er. This indicates that the slow magnetic relaxation is governed primarily by single-ion crystal-field effects rather than exchange coupling.
Barium-doped dual-pillar-stabilized calcium vanadate hydrate for high-performance aqueous zinc-ion batteries.
Chen Z, Dong Y
Dalton Trans · 2026 Jul · PMID 42383556 · Publisher ↗
To meet the stringent requirements for safety, sustainability, and cost-effectiveness in large-scale energy storage systems, aqueous zinc-ion batteries (AZIBs) have attracted considerable attention in recent years. Howev...
To meet the stringent requirements for safety, sustainability, and cost-effectiveness in large-scale energy storage systems, aqueous zinc-ion batteries (AZIBs) have attracted considerable attention in recent years. However, layered vanadium oxides, some of the most promising cathode materials, often suffer from structural degradation and sluggish kinetics during cycling, which severely limits the overall performance of the batteries. Herein, we regulate the interlayer architecture of calcium vanadate hydrate (CaVO·4HO, CVO) through partial substitution with large-radius Ba, forming CaBaVO·4HO (CBVO). The incorporation of Ba expands the interlayer spacing while preserving the layered framework, establishing a dual-pillar configuration with Ca that balances structural rigidity and lattice adaptability. This structural modulation lowers the Zn migration barrier and suppresses strain accumulation during repeated insertion/extraction. As a result, the optimized CBVO electrode exhibits fast, reversible Zn storage with a high specific capacity of 360.9 mAh g at 0.1 A g and maintains 91% capacity retention after 3500 cycles at 5 A g. Kinetic analysis reveals a transition toward pseudocapacitive behavior, while XRD identifies a reversible Zn/H co-intercalation mechanism. This work establishes interlayer cation engineering as a general strategy for high-rate and durable multivalent ion storage.
Organoruthenium(II) complexes appended with racemic pyrazoline ligands: integrated experimental and theoretical insights revealing their apoptotic efficacy.
Manimuthu A, Bhuvanesh NSP, Nallasamy D
Dalton Trans · 2026 Jul · PMID 42383459 · Publisher ↗
Herein, we report four new cationic ruthenium(II)-(-cymene) racemic complexes (C1-C4) containing N,S-coordinated pyrazoline ligands. The contemplated organoruthenium compounds from dimeric Ru(II)-(η-cymene) chlorido moie...
Herein, we report four new cationic ruthenium(II)-(-cymene) racemic complexes (C1-C4) containing N,S-coordinated pyrazoline ligands. The contemplated organoruthenium compounds from dimeric Ru(II)-(η-cymene) chlorido moieties and pyrazoline-based ligands were synthesized and characterized using standard analytical, spectral and ESI-HRMS data. The pseudo-octahedral geometry, neutral bidentate N and S chelation of pyrazoline thiosemicarbazones, and cationic nature of all four complexes were confirmed through single-crystal X-ray diffraction (SC-XRD) study. The geometry of individual enantiomers of the respective enantiomeric pairs was optimized using density functional theory. Furthermore, frequency calculations, single-point calculations, frontier molecular orbital analysis and TD-DFT were also carried out. Biomolecular interactions of the complexes were investigated using UV-visible and fluorescence spectroscopy techniques with calf-thymus DNA (CT-DNA) and bovine serum albumin (BSA). Anticancer activity of the racemic complexes C1-C4 against human colorectal adenocarcinoma (HT-29) and human lung cancer (A549) cell lines assessed using MTT assay indicated the IC concentrations ranging from 15.39 to 21.86 µM and 17.29 to 24.29 µM for HT-29 and A549 cells, respectively, and the values are comparable to that of the positive control (cisplatin) and also the same assay was performed on human epithelial kidney cells (HEK-293) to determine the selectivity index of the complexes. As these four complexes possess similar molecular structures, based on the better selectivity index and promising performance, complex C2 was selected for more detailed anticancer assays. DAPI, DCFDA, and JC-I cellular staining assays, along with flow cytometry, were performed on C2-treated A549 cells. The complex C2 induced apoptosis through DNA damage, ROS generation, and mitochondrial depolarization. Molecular docking studies on the DFT-optimized and conformers of the complexes were undertaken towards a spectrum of cancer-related protein targets to validate their binding interactions. The complexes demonstrated favorable binding interactions with B-DNA, BSA, cyclooxygenase-2 (COX-2) and B-cell lymphoma-2 (Bcl-2), with high binding affinity values of -8.12, -6.6, -6.25 and -7.53 kcal mol, respectively. Simultaneously, binding interactions of the individual enantiomers ( and ) of the respective pairs of each complex towards the target proteins were also examined, but they did not vary greatly among the complexes.
Nickel and platinum modified exfoliated carbon nitride as photo-thermal catalysts for CO hydrogenation.
Hou H, Rana AG, Minceva M … +12 more , Gil-Sepulcre M, Rüdiger O, DeBeer S, Garzón Manjón A, Botifoll M, Ramasse Q, Arbiol J, Romero N, Sala X, García-Antón J, Tasbihi M, Fresno F
Dalton Trans · 2026 Jul · PMID 42383444 · Publisher ↗
The photocatalytic conversion of carbon dioxide into value-added fuels and chemicals is a promising route to mitigate greenhouse gas emissions while enabling sustainable energy storage. This study investigates the use of...
The photocatalytic conversion of carbon dioxide into value-added fuels and chemicals is a promising route to mitigate greenhouse gas emissions while enabling sustainable energy storage. This study investigates the use of catalysts composed of exfoliated graphitic carbon nitride modified with either single-atom Ni sites or Pt nanoparticles for photo-thermal CO hydrogenation under combined light irradiation and thermal activation. The photocatalysts have been extensively characterized by different physico-chemical techniques, allowing the study of structure-activity relationships. Both metal-modified catalysts exhibit significantly enhanced CO conversion compared to pristine g-CN, which is attributed to improved light absorption, reduced charge recombination, and the role of metals as catalytically active sites. However, the catalytic behaviour varies markedly depending on the metal. Pt nanoparticles promote a thermally driven pathway assisted by light, enhancing overall activity and favouring CO formation, whereas Ni single-atom sites preserve the photocatalytic character of the support and shift the selectivity of hydrogenation towards methanol rather than methane primarily obtained over metal-free CN. These findings indicate that the combined photonic and thermal energy inputs efficiently activate both CO and H, accelerating reaction kinetics and modifying reaction pathways beyond those achieved in purely thermal or purely photocatalytic systems.
Synthesis of filled β-Mn-type ternary tellurides using a boron-tellurium reaction mixture.
Chirantha Edirisinghe EA, Jana S, Gabilondo EA … +2 more , Shiv Halasyamani P, Maggard PA
Dalton Trans · 2026 Jul · PMID 42383443 · Publisher ↗
The synthetic discovery of new metal-telluride phases remains challenging due to the limitations of stabilizing increasingly complex compositions using conventional solid-state reactions. Described herein, a boron-tellur...
The synthetic discovery of new metal-telluride phases remains challenging due to the limitations of stabilizing increasingly complex compositions using conventional solid-state reactions. Described herein, a boron-tellurium mixture (BTM) reaction is demonstrated to provide an effective route to synthetically access ternary telluride phases within the alkali-triel-telluride (A-Tr-Te, A = alkali metal, Tr = Ga or In) compositional space. High quality single crystals and polycrystalline phases of the new NaInTe (1) and NaGaTe (2) were prepared and structurally characterized by single crystal and powder X-ray diffraction techniques. These isostructural analogues crystallize in the noncentrosymmetric and chiral space group 32, exhibiting three-dimensionally condensed TrTe tetrahedra with a filled β-Mn-type network. Diffuse reflectance spectroscopy reveals that both are small bandgap semiconductors, with direct optical bandgaps of 1.18 eV and 0.79 eV for 1 and 2, respectively. Compound 1 exhibits a weak second-harmonic generation response under stimulation by a Ho:YAG laser at 2090 nm. Density functional theory calculations show that the valence band maximum is dominated by Te 5p states in both 1 and 2. Conversely, the conduction band states stem from mixed contributions of Tr and Te orbitals. These results provide the first experimental evaluation of the optical properties of the Na-Tr-Te (Tr = Ga, In) 1 : 3 : 5 telluride compounds, providing insights into the electronic structure and nonlinear optical properties of stuffed β-Mn-type telluride frameworks.
Radical switching Am/Eu selectivity in sterically restricted diglycolamides.
Kalinin MA, Evsiunina MV, Kalle P … +2 more , Matveev PI, Borisova NE
Dalton Trans · 2026 Jul · PMID 42383435 · Publisher ↗
Eight new bisoxolactams were prepared from 5-valerolactone and the corresponding amines. A protocol was developed for producing symmetrical and asymmetrical extractants for the separation of Am(III) and Eu(III). It was f...
Eight new bisoxolactams were prepared from 5-valerolactone and the corresponding amines. A protocol was developed for producing symmetrical and asymmetrical extractants for the separation of Am(III) and Eu(III). It was found that the efficiency of the extractant can be adjusted by tuning the softness of the ligands. Adding bulky groups such as -butyl reverses the extraction preference of the diglycolamide-type reagent, leading to preferential extraction of americium(III) over europium(III).
Polyoxometalate immobilized on sulfur-vacancy-engineered ZnInS/tubular carbon nitride for efficient photocatalytic hydrogen evolution.
Wen X, Wang X, Guo X … +6 more , Li G, Zhao N, Duan X, Pang H, Li L, Ma H
Dalton Trans · 2026 Jul · PMID 42381581 · Publisher ↗
To address the low separation efficiency of photogenerated charge carriers, which restricts photocatalytic water splitting, multi-component synergistic ternary photocatalysts were rationally designed. Hollow tubular carb...
To address the low separation efficiency of photogenerated charge carriers, which restricts photocatalytic water splitting, multi-component synergistic ternary photocatalysts were rationally designed. Hollow tubular carbon nitride (TCN, tubular carbon nitride) was used as the substrate, zinc indium sulfide (ZnInS, ZIS) rich in sulfur vacancies (Vs) was integrated with TCN, and dopamine (PDA), which acted as both an adhesive and interface modifier, was employed to load polyoxometalates ([Co(HO)(PWO)], PWCo and [Ni(HO)(PWO)], PWNi) onto Vs-ZIS/TCN, yielding the ternary PWCo/Vs-ZIS/TCN and PWNi/Vs-ZIS/TCN composites. Systematic characterizations (PXRD, FT-IR spectroscopy, and XPS) confirmed the successful synthesis of these composites, with the existence of stable Vs and inter-component interactions, and N adsorption-desorption revealed their mesoporous structure (PWCo/Vs-ZIS/TCN-75: 62.59 m g) with abundant active sites. Optical and electrochemical tests showed that the ternary composites had enhanced visible-light absorption and photogenerated carrier separation efficiency compared with their binary counterparts. Photocatalytic hydrogen evolution experiments indicated that PWCo/Vs-ZIS/TCN-75 had the highest hydrogen evolution rate (11.50 mmol g h, 2.98 times that of Vs-ZIS/TCN-100) and excellent long-term stability (14.3% activity decay after 30 h of cyclic testing). Mechanistic analysis attributed the improved performance to the synergistic effect of the Z-scheme heterojunction, PDA interface modification and Vs-mediated carrier capture. This work provides a feasible approach for the development of high-performance photocatalytic systems and insights for the rational design of efficient, stable multi-component photocatalysts for solar-driven hydrogen production.
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