Dalton Trans [JOURNAL]
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200 papers
Pure reduced polyoxometalate materials as electroactive materials for assembling proton energy storage devices.
Wang C, Guo WH, Tang W … +5 more , Cui YZ, Qi ZP, Liang S, Zang HY, Su ZM
Dalton Trans · 2026 Jun · PMID 42359821 · Publisher ↗
The integration of efficient proton transport and reversible redox activity in a single material is highly desirable for advanced electrochemical devices, yet remains challenging. Herein, two novel crystalline pyridine-d...
The integration of efficient proton transport and reversible redox activity in a single material is highly desirable for advanced electrochemical devices, yet remains challenging. Herein, two novel crystalline pyridine-decorated polyoxometalates, namely (1) and V6 (2), are designed and synthesized a hydrothermal route. The pyridine molecules endow the materials with remarkable proton conductivity, reaching 9.63 × 10 S cm (1) and 2.21 × 10 S cm (2) at 85 °C and 95% RH. The excellent proton conduction stems from the ordered hydrogen-bonding networks facilitated by both the pyridine N sites and the terminal/surface oxygen atoms of the {PMoV6O} anions. Furthermore, the title complexes as electrochemically active materials are loaded onto the surface of carbon paper to assemble solid-state proton energy storage devices; the 1-CP@PANI-SC devices can achieve an outstanding specific capacitance of 330.12 F g and cycling stability of 94.2% after 1000 cycles. Crucially, electrochemical analysis coupled with proton conduction studies indicates that the pre-established proton-conducting pathways significantly facilitate the transport of charge-compensating protons (H) during the rapid redox reactions of molybdenum centers, thereby enhancing the pseudo-capacitive kinetics and overall electrochemical efficiency. This work not only presents high-performance multifunctional electroactive materials but also establishes a material design principle that links proton conduction with charge storage dynamics for next-generation energy storage systems.
Strain-specific synergy: an oxo-rhenium(V) complex potentiates antibiotic efficacy in strains.
Demirci G, Cortat Y, Crochet A … +3 more , Calia E, Sprecher SG, Zobi F
Dalton Trans · 2026 Jun · PMID 42359818 · Publisher ↗
In this study, a library of oxo-rhenium(V) complexes of general formula [ClReO(NN)] bearing diimine ligands was synthesized and fully characterized. The complexes were evaluated for antibacterial activity against Gram-po...
In this study, a library of oxo-rhenium(V) complexes of general formula [ClReO(NN)] bearing diimine ligands was synthesized and fully characterized. The complexes were evaluated for antibacterial activity against Gram-positive and Gram-negative bacteria (MSSA, MRSA, , and ). Increasing the lipophilicity of the diimine ligand led to an enhancement in biological activity. The most active compound, bearing NN = bathocuproine (complex 9), exhibited potent activity against strains (MIC = 2 µM). Its toxicity profile was assessed and : cytotoxicity toward L929 fibroblasts afforded a therapeutic index (TI) of 4.9, while evaluation in the invertebrate model showed only 12.9% lethality at 4× MIC after 24 h, indicating a favorable preliminary safety profile. Mechanistic investigations in MSSA and MRSA revealed strain-specific synergistic interactions of 9 with chloramphenicol and tetracycline in MSSA, and with ampicillin in MRSA, increasing the therapeutic index up to 19.5. Notably, co-administration of sub-inhibitory concentrations of ampicillin and 9 suppressed MRSA growth for more than 72 h. Computational studies suggest that complex 9 may interfere with the β-lactam resistance pathway in MRSA.
CaSnO perovskite oxide: influence of Bi doping on structural, optical, and magnetic properties.
M A, S L, S B … +1 more , M M
Dalton Trans · 2026 Jun · PMID 42359771 · Publisher ↗
In the present study, the structural, optical, and room-temperature magnetic properties of undoped and Bi-doped CaSnO (CSO) perovskite samples were systematically investigated. The samples were synthesised a chemical pr...
In the present study, the structural, optical, and room-temperature magnetic properties of undoped and Bi-doped CaSnO (CSO) perovskite samples were systematically investigated. The samples were synthesised a chemical precipitation method. X-ray diffraction (XRD) analysis revealed the crystal structure and variations in lattice parameters, with a significant reduction in crystallite size from 60 nm in the undoped sample to 21 nm in the Bi-doped CSO, indicating the inhibitory effect of Bi incorporation on crystal growth. Metal oxide vibrations and defects such as oxygen vacancies (V) arising from bismuth doping were characterized through Fourier-transform infrared (FTIR) and Raman spectroscopy. Ultraviolet-visible (UV-Vis) absorption studies demonstrated a decrease in the optical band gap from 4.25 eV (undoped) to 3.73 eV (Bi-doped), while photoluminescence (PL) measurements confirmed the presence of defect-induced states. Electron paramagnetic resonance (EPR) spectra further corroborated the existence of defect sites and F-centers within the lattice. Undoped CSO exhibited a weak ferromagnetic component superimposed on a dominant diamagnetic response. Upon Bi doping, subtle magnetic interactions emerged, with 3% of Bi doped CSO demonstrating a ferromagnetic behaviour of 2.6 × 10 emu g, which can be explained based on an -centre exchange mechanism.
Revisiting synthesis of pure chernobylite solid solutions for thermal stability investigations.
Avallone A, Carette L, Estevenon P … +10 more , Yot PG, Hennig C, Bright EL, Podor R, Goff XL, Pinho PVB, Clavier N, Guo X, Guéneau C, Dacheux N
Dalton Trans · 2026 Jun · PMID 42359686 · Publisher ↗
A multiparametric study was developed to optimize the hydrothermal synthesis of chernobylite solid solutions (ZrUSiO), a phase first discovered in the Elephant's foot of the Chernobyl nuclear power plant following the 19...
A multiparametric study was developed to optimize the hydrothermal synthesis of chernobylite solid solutions (ZrUSiO), a phase first discovered in the Elephant's foot of the Chernobyl nuclear power plant following the 1986 nuclear accident. The goal was to obtain phase-pure samples for thermodynamic investigation. Optimal synthesis conditions were determined starting from uranium (IV) and zirconium (IV) chloride precursors, using a hydrothermal treatment for seven days at 250 °C with a reaction medium maintained within a pH range of 1.4 to 1.8, which minimized the formation of secondary phases Under these conditions, solid solutions of chernobylite were synthesized up to = 0.80. However, the systematic presence of residual oxide phases in the samples required the development of a purification process involving alternating leaching steps in basic and acid media. This process removed amorphous silica and selectively dissolved residual oxide phases, respectively. This protocol yielded pure ZrUSiO samples over a wide range of compositions ( ≤ 0.6). The resulting powders consisted of spherical agglomerates of approximately 300 µm in diameter, with specific surface areas ranging from 19 to 22 m g. Finally, the thermal stability of the chernobylite solid solutions was evaluated using heat treatments between 1000 °C and 1300 °C. All samples, except for those most enriched in uranium, proved to be thermally stable even at 1300 °C.
[RbCl][CdInSe]: a salt inclusion chalcogenide with a diamond-like framework for infrared nonlinear optics.
Xie P, Ren Q, Feng J … +2 more , Du H, Mi S
Dalton Trans · 2026 Jun · PMID 42347964 · Publisher ↗
The macroscopic nonlinear optical (NLO) response of T2 supertetrahedra strongly depends on their arrangement in the crystal lattice. Without effective symmetry control, disordered spatial orientations of these building u...
The macroscopic nonlinear optical (NLO) response of T2 supertetrahedra strongly depends on their arrangement in the crystal lattice. Without effective symmetry control, disordered spatial orientations of these building units cause mutual cancellation of their microscopic hyperpolarizabilities, resulting in substantial reduction of the macroscopic NLO coefficients. Regulation of T2 supertetrahedron polymerization with alkali and alkaline earth metals has garnered extensive attention. Herein, we apply a strategy using zero-dimensional (0D) guest species in salt-inclusion chalcogenides (SICs) to influence coherent alignment of T2 supertetrahedra in the three-dimensional (3D) host framework. By tuning the 3D structural polymerization of the host [CdInSe] the 0D guest [RbCl] polycation, we successfully synthesized the SIC [RbCl][CdInSe]. Under the influence of the [RbCl] polycation, the T2 supertetrahedral units exhibit highly uniform orientational alignment. Experimental measurements and theoretical calculations reveal a bandgap of 1.70 eV, while first-principles calculations give NLO coefficients of = = -10.845 pm V, = = -9.957 pm V, and = 14.757 pm V. This work demonstrates the 0D-guest modulation of 3D-framework alignment and provides new avenues for designing high-performance infrared (IR) NLO crystals.
Direct electrochemistry as a mechanistic tool for studying engineered myoglobins: implications on carbene transferase activity.
Venckute E, Jarvis AG, Rodríguez-Maciá P
Dalton Trans · 2026 Jun · PMID 42333988 · Full text
Direct electrochemistry tools offer exclusive insight into the redox properties of metalloenzymes. However, they have not found widespread use within the artificial enzyme community, despite their potential to help infor...
Direct electrochemistry tools offer exclusive insight into the redox properties of metalloenzymes. However, they have not found widespread use within the artificial enzyme community, despite their potential to help inform catalyst design. Herein, we describe the use of a simple and robust method for non-covalent immobilisation of a library of myoglobin-based (Mb) engineered and cofactor-substituted metalloenzymes onto carbon electrodes. This allowed the determination of the reduction potentials () spanning M(III)/M(II) redox states for Fe and Mn Mb systems. In Fe-containing systems, more positive values matched higher carbene transferase activity under the tested conditions. For example, when = -10.6 mV ( standard hydrogen potential, SHE), a total turnover number (TTN) of 230 was observed, whereas when = -72.9 mV ( SHE), TTN = 16 in styrene cyclopropanation reactions. Additionally, we investigated the effect of active-site mutations on and the enantioselectivity of the enzymes. We found that a single mutation of residue 64 from histidine to glycine (H64G) reversed the enantiopreference of the enzyme. This proof-of-concept study highlights the use of direct electrochemistry as a fast and efficient mechanistic tool for characterising and informing the engineering of ArMs for applications in sustainable catalysis and electrochemical transformations.
Synthetic routes to PNC-heterocyclic cations.
Al-Zuhaika N, Chen J, Zelenco E … +1 more , Stephan DW
Dalton Trans · 2026 Jun · PMID 42333869 · Publisher ↗
While reactions of phosphino-phosphenium and phosphirenium cations with carbodiimides were explored, the combination of PPhCl, AlCl or K[B(CF)] and carbodiimides, dimines or imines, provided direct and general routes to...
While reactions of phosphino-phosphenium and phosphirenium cations with carbodiimides were explored, the combination of PPhCl, AlCl or K[B(CF)] and carbodiimides, dimines or imines, provided direct and general routes to salts of cationic five-membered PNC-rings.
Tuning the tetraarylcyclopentadienones of iron tricarbonyl complexes: effects on transfer hydrogenation and solubility.
Zingales E, Huertos MA, Sanchez-Cano C
Dalton Trans · 2026 Jun · PMID 42333831 · Publisher ↗
The nature of the ligands coordinated to the metal in cyclopentadienone iron tricarbonyl (CIC) complexes is important for the activation or H transfer steps of transfer hydrogenation (TH) catalysis. Previous reports show...
The nature of the ligands coordinated to the metal in cyclopentadienone iron tricarbonyl (CIC) complexes is important for the activation or H transfer steps of transfer hydrogenation (TH) catalysis. Previous reports showed an existing correlation between the electron-donating or -withdrawing nature of substituents appended to phenyl groups at 3,4 positions of tetraarylcyclopentadienones and the catalytic efficiency of the related CICs. Here we extend these studies to phenyl groups at positions 2,5. Our results show that careful selection of the substituent groups appended to the different aryl groups of tetraarylcyclopentadienones improves the solubility of CIC complexes in protic solvents and avoids the drastic reduction in catalytic efficiency for TH reactions showed by complexes carrying electron-withdrawing groups in their arene.
Ligand design controls biomolecule binding and cytotoxicity in platinum(II) complexes with ONS-type tridentate ligands.
Iskandrani A, Alezi D, Ali EMM … +6 more , Jedidi A, Alrashdi KS, Shkurenko A, Aljagthmi A, Eddaoudi M, Babgi BA
Dalton Trans · 2026 Jun · PMID 42333610 · Publisher ↗
Two types of ONS-tridentate ligands were obtained by condensation of salicylaldehyde derivatives with 2-(methylthio)aniline (L1-L6) or 2-(methylthio)ethylamine (L8 and L9) while -phenyl--diaminobenzene was used to create...
Two types of ONS-tridentate ligands were obtained by condensation of salicylaldehyde derivatives with 2-(methylthio)aniline (L1-L6) or 2-(methylthio)ethylamine (L8 and L9) while -phenyl--diaminobenzene was used to create the NNO-tridentate ligand (L7) for systematic studies. These ligands were used to generate nine platinum complexes (Pt1-Pt9). Single-crystal X-ray diffraction revealed that the O^N^S complexes adopt a conserved, slightly distorted square-planar geometry, largely unaffected by electronic variation of aryl substituents; N^N^O containing complexes have more distorted square planar structures. All the complexes exhibited good solution stability; P1-Pt6 behaved predominantly as neutral molecules in DMSO while P7-Pt9 showed higher tendencies for solvolysis. Lipophilicity (log ) was strongly ligand-dependent and increased with alkoxy substitution and halogenation. DNA-binding studies demonstrated strong, static interactions for the rigid, aromatic ONS-containing complexes, with intercalative or groove-assisted binding confirmed by viscosity measurements. Bromo- and ethoxy-substituted complexes showed the highest DNA affinity, whereas flexible ONS-analogues displayed weak binding. All complexes interacted favorably with bovine serum albumin through a static binding mechanism, suggesting possible interactions relevant to transport and distribution in biological media. Cytotoxicity evaluation against HepG2, HCT-116, and MCF-7 cancer cell lines revealed pronounced structure- and cell line-dependent cytotoxicity. Pt2 and Pt4 with their rigid ONS-containing ligands exhibited high potency and superior selectivity indices compared with cisplatin. Cell-cycle analysis showed that some complexes induce G2/M arrest, while the most active compounds (Pt2 and Pt4) promote apoptotic progression. Annexin V-FITC/PI assays confirmed apoptosis as the dominant mode of cell death, with Pt2 and Pt4 driving rapid late-stage apoptosis. The gene expression data highlight that the most effective complexes (Pt2 and Pt4) successfully combine proliferation arrest with a dominant pro-apoptotic signal. Overall, this work demonstrates that incorporation of a rigid, planar ONS-chelate represents a promising design strategy for developing platinum anticancer agents with enhanced selectivity and favorable biological performance.
A strontium alumanyl.
Pearce KG, Liu HY, McMullin CL … +1 more , Hill MS
Dalton Trans · 2026 Jul · PMID 42333409 · Publisher ↗
The strontium alumanyl, [(BDI)SrAl(SiN)], has been prepared from [(BDI)Sr(BPh)] and [(SiN)AlK]. Like its previously described calcium analogue, structural and computational analyses indicate that the Sr-Al interaction is...
The strontium alumanyl, [(BDI)SrAl(SiN)], has been prepared from [(BDI)Sr(BPh)] and [(SiN)AlK]. Like its previously described calcium analogue, structural and computational analyses indicate that the Sr-Al interaction is only marginally involved in the engagement of the Sr cation and alumanyl anion. Unlike its lighter equivalent, however, [(BDI)SrAl(SiN)] does not react with THF, the presence of which only appears to enhance its presumed dismutation and reaction with the toluene solvent at 100 °C to provide a strontium bis-hydrido(-tolyl)aluminate.
Synthesis and characterization of honeycomb-like carboxylate-bridged dimeric Cu(II) and Zn(II)-based coordination polymers with a pyridyl Schiff base linker: dye sorption and Schottky device applications.
Saha K, Jana SR, Das P … +7 more , Dutta B, Banerjee M, Naskar S, Jana NC, Hossain SS, Bera B, Sinha C
Dalton Trans · 2026 Jun · PMID 42329627 · Publisher ↗
The coordination polymers (CPs)/metal-organic frameworks (MOFs) incorporating hetero-bridging ligands have remarkable efficiency and versatility towards fulfilling the objectives of the Sustainable Development Goals (SDG...
The coordination polymers (CPs)/metal-organic frameworks (MOFs) incorporating hetero-bridging ligands have remarkable efficiency and versatility towards fulfilling the objectives of the Sustainable Development Goals (SDGs). In this aspect, two CPs, [Cu(3-bph)(adc)] (CP1) and [Zn(3-bph)(adc)] (CP2) (3-bph = (1,2)-1,2-bis(pyridin-3-ylmethylene)hydrazine and adc = 1-adamantanecarboxylate), are characterised, and their significant semiconducting property and selective dye sorption activity are explored. The CPs comprise a secondary building unit (SBU) of a carboxylate-bridging adc paddle-wheel, [M(adc)] (M = Cu(II), Zn(II)), which undergoes pyridyl-N linking by 3-bph to form a 1D chain, where the pyridyl rings undergo π-π interaction to construct a 2D honeycomb-supramolecular network. Interestingly, CP1 demonstrates the selective sorption of methyl red (MR) dye out of four dyes (methylene blue, rhodamine B, methyl red, and methyl orange) with a removal efficiency of 95.37% from aqueous solution within 1 h, whereas CP2 does not show measurable sorption activity. The sorption of CP1 fits the Langmuir isotherm ( = 0.9875) and follows pseudo-second-order kinetics, indicating chemisorption on a heterogeneous surface. The DFT calculations using crystallographic parameters determined the band gaps in the semiconducting region (2.39 eV (cal.) and 3.68 eV (exp.) for CP1 and 2.32 eV (cal.) and 3.65 eV (exp.) for CP2). This inspired the measurement of the electrical conductivity from a fabricated Schottky device with thin film electrodes, ITO/CPs/Al. The experiments show that CP2 (5.27 × 10 S m) has higher electrical conductivity than CP1 (2.72 × 10 S m) under identical conditions, which explains the superior charge-transport features of CP2 in comparison with CP1. These findings highlight that CP1 serves as a promising material for application as a sustainable MR dye removal agent from wastewater, while both CP1 and CP2 are potential candidates for semiconducting applications.
Advances and prospects of MIL-based drug delivery systems in the diagnosis and treatment of cervical cancer.
Zhang Y, Ye Y, Zhong Q … +7 more , Yan Z, Feng Z, Nezamzadeh-Ejhieh A, Jiang G, Pan Y, Gou Z, Liu J
Dalton Trans · 2026 Jun · PMID 42329079 · Publisher ↗
Cervical cancer, a common type of cancer with gynecological malignant tumors, poses a serious threat to women's health. Despite significant advances in cancer treatment, there is still a lack of effective early detection...
Cervical cancer, a common type of cancer with gynecological malignant tumors, poses a serious threat to women's health. Despite significant advances in cancer treatment, there is still a lack of effective early detection methods, and many therapeutic approaches suffer from low specificity and adverse side effects. Therefore, there is an urgent need to explore efficient diagnostic methods and targeted treatments with strong specificity and high efficacy. The Materials of Institute Lavoisier (MIL) family of materials possesses favorable porosity, large specific surface area, high drug-loading capacity, tunable pore sizes, and superior chemical stability. Notably, their satisfactory biocompatibility has further promoted their widespread research in cancer diagnosis and targeted therapy. Inspired by this, this review summarizes recent developments in the application of MIL materials in cervical cancer diagnosis and treatment. Primarily, the properties, structures, and synthesis methods of MIL materials, including MIL-100, MIL-101, MIL-88, and MIL-53, are introduced. Then, the application of MIL materials in the diagnosis of cervical cancer is discussed. MIL-based nanoplatforms for chemotherapy (CT), chemodynamic therapy (CDT), photothermal therapy (PTT), photodynamic therapy (PDT), and related combination therapies in cervical cancer treatment are reviewed. Finally, the challenges encountered in applying MIL materials in cervical cancer treatment are summarized, and prospects for their future development are provided.
Synthesis, characterisation and properties of a Cr(III) diphenyl quaterpyridine complex towards CO to CO reduction.
Kamashanju KC, Curtil M, Molton F … +3 more , Vlachopoulos N, Thomas F, Chauvin J
Dalton Trans · 2026 Jun · PMID 42328706 · Publisher ↗
During the last decade, group VI metals have regained interest in synthesizing inorganic complexes that demonstrate catalytic properties for CO reduction. However, these complexes often exhibit high overpotential and poo...
During the last decade, group VI metals have regained interest in synthesizing inorganic complexes that demonstrate catalytic properties for CO reduction. However, these complexes often exhibit high overpotential and poor efficiency compared to those constructed with less-abundant metals. In this work, a polypyridinyl complex consisting of a Cr(III) centre coordinated to the tetradentate ligand 4',4″-diphenyl-2,2':6',2″:6″,2‴-quaterpyridine and two monodentate chloride ligands ([Cr(dpqpy)Cl]) was synthesized and characterized. Cyclic voltammetry performed under argon displayed three quasi-reversible one-electron systems in the cathodic part. The Zn(II) parent complex ([Zn(dpqpy)Cl]) was also synthesized and investigated to identify the nature of the reduction events. The three reduced species of [Cr(dpqpy)Cl] were generated by exhaustive electrolysis and characterized by ultraviolet-visible and electron paramagnetic resonance spectroscopies. Density functional theory calculations confirmed that the last two reductions are localized on the quaterpyridine ligand. Under a CO atmosphere, with [Cr(dpqpy)Cl] dissolved in DMF in the presence of phenol, a catalytic current was observed during the last reduction at an onset potential of -1.72 V Ag/AgNO (10 M). Exhaustive electrolysis of [Cr(dpqpy)Cl] performed at -1.85 V under CO in DMF + 0.1 M TBAPF in the presence of 1.25 M phenol led to the formation of CO with a faradaic efficiency of 60% after 2 h, with no H being detected during the reaction time. Longer experiments led to a partial degradation of the complex.
Closed-loop hydrostannylation of white phosphorus using BuSnCl and NaBH: one-pot access to organophosphorus compounds.
Mende M, Heidkamp L, Wolf R … +1 more , Scott DJ
Dalton Trans · 2026 Jun · PMID 42325165 · Publisher ↗
The direct functionalization of white phosphorus (P) is gaining attention as an alternative to state-of-the-art multi-step processes. The hydrostannylation of P affords valuable monophosphorus compounds directly a hydro...
The direct functionalization of white phosphorus (P) is gaining attention as an alternative to state-of-the-art multi-step processes. The hydrostannylation of P affords valuable monophosphorus compounds directly a hydrostannylphosphine mixture (BuSn)PH (where = 0-3) that reacts with suitable electrophiles. However, previous reports required terminal reductants which are infeasible for industrial-scale applications. Here, we report an improvement in this chemistry using NaBH as the terminal reducing agent, generating the key hydrostannylation agent BuSnH from BuSnCl. The resulting (BuSn)PH mixtures were successfully functionalized towards useful P compounds. Furthermore, we present the 'one-pot' preparation of tetrakis(hydroxymethyl)phosphonium chloride (THPC), the subsequent direct recycling of BuSnCl, and preliminary attempts towards the catalytic synthesis of THPC.
Correction: Dodecanuclear [NiII8Ln] clusters and rings of corner-sharing {NiII2Ln} cubanes (Ln = Dy, Gd, Y); magnetic and magnetothermal properties.
Tziotzi TG, Agapaki E, Charkiolakis EK … +6 more , Gracia D, Ubach I Cervera M, Dalgarno SJ, Evangelisti M, Brechin EK, Milios CJ
Dalton Trans · 2026 Jul · PMID 42325154 · Publisher ↗
Correction for 'Dodecanuclear [NiII8Ln] clusters and rings of corner-sharing {NiII2Ln} cubanes (Ln = Dy, Gd, Y); magnetic and magnetothermal properties' by Thomais G. Tziotzi , , 2025, , 4664-4671, https://doi.org/10.103...
Correction for 'Dodecanuclear [NiII8Ln] clusters and rings of corner-sharing {NiII2Ln} cubanes (Ln = Dy, Gd, Y); magnetic and magnetothermal properties' by Thomais G. Tziotzi , , 2025, , 4664-4671, https://doi.org/10.1039/D5DT00175G.
New insights into the photocatalytic properties of composites based on TiO and single-walled carbon nanotubes.
Udrescu A, Smaranda I, Cercel R … +6 more , Androne A, Nila A, Matei E, Mercioniu I, Bellucci S, Baibarac M
Dalton Trans · 2026 Jun · PMID 42325127 · Publisher ↗
Composites based on TiO and single-walled carbon nanotubes (SWCNTs), highly separated in semiconducting tubes (S-SWCNTs) and as a mixture of metallic and semiconducting tubes (M + S-SWCNTs), were obtained by the interact...
Composites based on TiO and single-walled carbon nanotubes (SWCNTs), highly separated in semiconducting tubes (S-SWCNTs) and as a mixture of metallic and semiconducting tubes (M + S-SWCNTs), were obtained by the interaction in the solid state. This interaction induces a change in the size of TiO particles from 23.67 nm to 28.2 and 150 nm, respectively, accompanied by an increase in the disorder state of the graphitic lattice of SWCNTs. We demonstrate by UV-VIS spectroscopy that the best performance in terms of rhodamine 6G (Rh6G) photodegradation is obtained in the case of the TiO/S-SWCNT composite. The highest values of the Rh6G photodegradation efficiency were equal to 92% for an S-SWCNT concentration in the photocatalyst mass of 10 wt% and 94% for a 0.1 mM Rh6G solution with a pH equal to 1. We demonstrate that an important role is played by the O˙ and ˙OH species in the photodegradation mechanism of Rh6G. This study contributes to a better understanding of the role of metallic and semiconducting carbon nanotubes in the photocatalysis field, highlighting that composites based on semiconducting SWCNTs and semiconducting metallic oxides are those that contribute essentially to the removal of dyes by exposure to the light emitted by a halogen lamp.
Weakly coordinating borophosphates - CaM(HO)[B(PO)]·HO (M = Mg, Mn, Co, Zn, Cd).
Wessels V, Mikuta M, Höppe HA
Dalton Trans · 2026 Jun · PMID 42325060 · Publisher ↗
Up to now, a considerable number of borophosphates have been reported, despite the young history of this material class. However, detailed Tanabe-Sugano analyses to investigate the coordination strength of the host struc...
Up to now, a considerable number of borophosphates have been reported, despite the young history of this material class. However, detailed Tanabe-Sugano analyses to investigate the coordination strength of the host structures have barely been reported yet. Herein, the series CaM(HO)[B(PO)]·HO with M = Ni, Fe was extended by introducing further metal cations with M = Mg, Mn, Co, Zn, Cd; the M atoms are coordinated octahedrally by oxygen and water. Thus, the reflection spectra for M = Mn, Co were elucidated by determining the Racah parameter and the ligand field splitting of the d-orbitals which revealed that borophosphates can be classified as weakly coordinating host materials. The crystal structure contains corner sharing borate and phosphate tetrahedra forming one-dimensional helical chains with water molecules inside those helices. Single-crystal data revealed the presence of systematically absent reflections in the original space group 622 which was solved by losing the twofold axis, whereby the structure was refined in the trigonal subgroup 321. Next to single-crystal XRD and UV-vis spectroscopy, the titled compounds were further characterised by powder XRD, FT-IR spectroscopy and thermal analysis.
Optimization of Fe(III)-based negative electrodes for lithium-ion batteries: probing electrochemical performance and stability characteristics.
Singh T, Varshney G, Hans S … +2 more , Sengupta S, Chakraborty S
Dalton Trans · 2026 Jun · PMID 42319284 · Publisher ↗
The development of inexpensive and sustainable electrode materials is essential for advancing next-generation lithium-ion batteries (LIBs). In this study, we report an investigation of an Earth-abundant Fe(III)-based mol...
The development of inexpensive and sustainable electrode materials is essential for advancing next-generation lithium-ion batteries (LIBs). In this study, we report an investigation of an Earth-abundant Fe(III)-based molecular complex incorporating a hydrazyl pyridine framework (C-1) as an anode material for LIB applications. The synthesized C-1 electrode delivers a promising initial discharge capacity of 1182.18 mAh g and a reversible charge capacity of 384.27 mAh g with an initial coulombic efficiency of 32.5%. The discharge profile subsequently shows a stable, reversible capacity of 393.40 mAh g, confirming efficient lithium-ion storage within the molecular framework. Furthermore, the electrode shows a moderate rate capability, a reversible capacity of 113.40 mAh g after 100 cycles, and a stable coulombic efficiency during long-term cycling. The observed electrochemical behaviour indicates that the hydrazyl-pyridine-coordinated Fe(III) architecture is structurally robust and promotes charge transport during repeated lithiation/delithiation processes. We demonstrate that Fe-based molecular complexes could be promising, affordable, and chemically tunable candidate electrodes, opening up avenues for sustainable and low-cost energy storage solutions.
β-Diketonate-bearing half-paddlewheel-type diruthenium(II,II) naphthyridine complexes with well-defined Ru-Ru double bonds.
Kataoka Y, Tada N, Yano N … +1 more , Handa M
Dalton Trans · 2026 Jun · PMID 42319276 · Publisher ↗
Three new diruthenium(II,II) naphthyridine complexes with β-diketonate ligands, [Ru(npc)(L)] (npc = 1,8-naphthyridine-2-carboxylate, L = acetylacetonate (acac) for 2, hexafluoroacetylacetonate (hfac) for 3, and 1,3-diphe...
Three new diruthenium(II,II) naphthyridine complexes with β-diketonate ligands, [Ru(npc)(L)] (npc = 1,8-naphthyridine-2-carboxylate, L = acetylacetonate (acac) for 2, hexafluoroacetylacetonate (hfac) for 3, and 1,3-diphenyl-1,3-propanedionate (dppd) for 4), were successfully synthesized solvothermal reactions of [Ru(npc)(OCMe)] (1) with the corresponding β-diketone ligands. Crystallographic analyses revealed that 2-4 commonly adopt half-paddlewheel-type structures, which feature (i) a direct Ru-Ru double bond (2.3671(2), 2.3742(4), and 2.3587(5) Å, respectively), (ii) two npc ligands bridging the Ru core in head-to-tail fashion, and (iii) two β-diketonate ligands chelating each Ru ion. Temperature-dependent magnetic susceptibility measurements revealed that 2-4 exhibit effective magnetic moments of 2.85, 2.75, and 2.80 at 300 K, respectively, which are consistent with the spin-only value of 2.83 for an = 1 system, and large zero-field splitting parameters ( = 235, 345, and 235 cm, respectively), which are commonly observed for paddlewheel-type Ru complexes. Spin-density distributions and molecular orbital analyses based on density functional theory (DFT) calculations clarified that (a) two magnetic spins in 2-4 are predominantly localized on the Ru core, (b) the electronic configuration of the Ru core is commonly πδσδ*π*, and (c) the LUMO(β)s of 2 and 4 are mainly derived from the π*(npc) orbitals, whereas that of 3 is primarily composed of the π*(Ru)/π*(hfac) orbital. Electrochemical properties are strongly influenced by the β-diketonate ligands; 3 exhibits a markedly positive shift of the oxidation wave attributed to the Ru/Ru redox couple compared with 2 and 4, owing to the strong electron-withdrawing effect of the hfac ligand. Furthermore, a Ru/Ru redox couple was observed for 3 at -0.37 V, whereas the corresponding reduction waves were not detected for 2 and 4. The absorption spectra of 2 and 4 exhibit intense bands in the 550-750 nm region, which are attributed to MLCT transitions from the Ru moiety to the npc ligands, and are similar to that of 1. In contrast, the absorption bands of 3 observed in the 502-630 nm region, which are significantly blue-shifted by 50-120 nm relative to those of 2 and 4 due to the strong electron-withdrawing effect of the CF group in the hfac ligand, were assigned to MLCT transitions from the Ru core to the npc ligands as well as the hfac ligands based on time-dependent DFT calculations.
Unveiling the n → π* interactions in main-group carbonyl complexes.
Deo G, Tiwari MK
Dalton Trans · 2026 Jun · PMID 42318798 · Publisher ↗
n → π* interactions have been widely explored in organic compounds, biomolecules, and transition metal complexes. However, they remain largely unexplored in main-group carbonyl systems. Herein, we report n → π* interacti...
n → π* interactions have been widely explored in organic compounds, biomolecules, and transition metal complexes. However, they remain largely unexplored in main-group carbonyl systems. Herein, we report n → π* interactions between oxygen-based Lewis bases and their S- and Se-analogs with the beryllium tricarbonyl and borylene dicarbonyl complexes, Be(CO) and BH(CO), using density functional theory. The donors interact with these complexes through the region between the two carbonyl groups, in a nearly planar geometry. Analyses based on the quantum theory of atoms in molecules (QTAIM) and the noncovalent interaction (NCI) index reveal a double-faced noncovalent interaction between the donor and the two carbonyl groups in the above complexes. These analyses further indicate that the donors do not interact with these complexes through their central atoms, Be or B. Natural bond orbital (NBO) analysis further indicates that these interactions exhibit the key characteristics of n → π* interactions, involving the delocalization of the lone-pair electron density from a donor atom into the antibonding (π*) orbital of the carbonyl groups. The calculated interaction energies, second-order perturbation energies associated with charge transfer, and the associated geometrical parameters support this electron delocalization, reinforcing its resemblance to the nucleophilic character of the electron donor typically observed in n → π* interactions.
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