Félix G, Selikhov AN, Kallio M
… +6 more, Vieru V, Vologzhanina AV, Balagurova EV, Guari Y, Larionova J, Trifonov AA
Dalton Trans
· 2026 Jun · PMID 42210907
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We report the synthesis, structures, and magnetic properties of two Dy complexes supported by a tripodal tris(aryl)alkoxide ligand (MeNCH--CH)CO. The mononuclear complex [κ-O,N,N-(MeNCH--CH)CO]DyCl(THF) (1) adopts a dist...We report the synthesis, structures, and magnetic properties of two Dy complexes supported by a tripodal tris(aryl)alkoxide ligand (MeNCH--CH)CO. The mononuclear complex [κ-O,N,N-(MeNCH--CH)CO]DyCl(THF) (1) adopts a distorted octahedral geometry, while its reaction with a dipotassium dicarbollide K[7,8-MeCBH] affords a heterobimetallic coordination polymer {[K(μ-Cl)Dy(κ-O,N,N-(MeNCH--CH)CO)(μ-2,3-MeCBH)]·0.5THF} (2·0.5THF) featuring a layered structure. Both compounds exhibit single-molecule magnet (SMM) behavior, with effective barriers of 344 K (240 cm) for 1 and 133 K (92.5 cm) for 2. calculations indicate that 1 relaxes the third excited Kramers doublet (KD), while 2 likely relaxes through the second KD. The relaxation pathways observed experimentally for 2 do not correspond to the computed KDs, possibly due to experimental limitations at high temperatures or fast relaxation rates undetectable by alternating current susceptibility.
Dalton Trans
· 2026 Jun · PMID 42210755
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Hybrid organic-inorganic crystals are attractive due to their large structural diversity and easy fabrication. Polyoxometalates, including polyoxovanadates (POVs), have gained interest for biomedical or battery applicat...Hybrid organic-inorganic crystals are attractive due to their large structural diversity and easy fabrication. Polyoxometalates, including polyoxovanadates (POVs), have gained interest for biomedical or battery applications and they can be prepared with a plethora of cationic matrices to balance the anionic charge of the metal-oxo cluster. Here, we employ a simple solvothermal synthesis to produce hybrid organic-inorganic crystals between the anionic "inorganic" vanadate and the cationic "organic" metal-ethylenediamine (en) complexes [M(en)]. A series of different 3d metals were tested with Co (reported in a previous publication), Ni, Cu and Zn, producing crystals of high enough quality for single crystal X-ray diffraction structure investigation Co, preferring the +3 oxidation state, forms crystals in the supernatant between [Co(en)] and 1D (VO) POVs with chains of corner-sharing (VO)-tetrahedra. The other 3d metals, Ni, Cu and Zn, prefer the +2 oxidation state and form crystals in the precipitate with mixed oxidation state (V/V) spherical (VO) or (VO) molecular POVs. The (VO) or (VO) POV morphology is selectively tuneable by pH when using the amphoteric Zn precursor. We report the crystal structures of 4[Ni(en)]·(VOCl)·13.26(HO), 4[Cu(en)]·(VOCl)·4(HO), and a high-quality structure of 2[Zn(en)(enH)](VOCl)(enH)·5.63 HO crystallizing in the orthorhombic space group .
Yuan S, Zhang L, Du H
… +5 more, Zhu C, Xie H, Cao Y, Sheng J, Li Y
Dalton Trans
· 2026 Jun · PMID 42207127
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In this study, a uniformly dispersed CoO catalyst supported on nickel foam was synthesized a flame combustion method. At -0.7 V ( RHE), the catalyst demonstrates an ammonia production rate of 2.96 mmol hcm, accompanied...In this study, a uniformly dispersed CoO catalyst supported on nickel foam was synthesized a flame combustion method. At -0.7 V ( RHE), the catalyst demonstrates an ammonia production rate of 2.96 mmol hcm, accompanied by a faradaic efficiency approaching 100% during the nitrate reduction reaction. Theoretical calculations reveal that the introduction of the nickel support induces electron transfer from Ni to Co, thereby reducing the desorption energy barrier for adsorbed NH and consequently enhancing the catalytic activity.
Maliuzhenko V, Weselski M, Książek M
… +5 more, Hochdörffer T, Wolny JA, Schünemann V, Kusz J, Bronisz R
Dalton Trans
· 2026 Jun · PMID 42206953
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Reactions of the ditopic ligands 1-(5-(2-pyridyl)tetrazol-1-yl)-3-(tetrazol-2-yl)propane (5-p1tz2tz), 1-(5-(2-pyridyl)tetrazol-2-yl)-3-(tetrazol-2-yl)propane (5-p2tz2tz), and 1-(3-(2-pyridyl)-1,2,4-triazol-1-yl)-3-(tetra...Reactions of the ditopic ligands 1-(5-(2-pyridyl)tetrazol-1-yl)-3-(tetrazol-2-yl)propane (5-p1tz2tz), 1-(5-(2-pyridyl)tetrazol-2-yl)-3-(tetrazol-2-yl)propane (5-p2tz2tz), and 1-(3-(2-pyridyl)-1,2,4-triazol-1-yl)-3-(tetrazol-1-yl)propane (3-p1tr1tz) with iron(II) tetrafluoroborate afforded a series of one-dimensional coordination polymers: [Fe(5-p1tz2tz)](BF) (1), [Fe(5-p2tz2tz)](BF) (2), [Fe(3-p1tr1tz)](BF)·CHCN (3) and [Fe(3-p1tr1tz)](BF)·CHOH (4). The first coordination spheres of all complexes are composed of two chelating pyridylazole units and two tetrazole rings. The two complexes involving pyridyltetrazole-form 1D chains with -coordinated monotetrazoles. They exhibit gradual spin transitions centred at approximately 350 K. For the pyridyl-1,2,4-triazole ligand, two polymorphs were isolated. One compound is a structural analogue of pyridyltetrazole complexes and exhibits high-spin down to 10 K. Modifying the synthetic procedure yields a 1D zig-zag chain with almost the same molecular volume, but with -coordinated monodentate tetrazole. This complex exhibits an abrupt spin-crossover accompanied by a hysteresis loop ( = 114 K, = 131 K). Density functional theory (DFT) modelling of the above systems, combined with results for known mononuclear and polynuclear complexes of 1-propyltetrazole revealed how the spin-transition energies vary from the mononuclear species to the corresponding 1D chains.
Dalton Trans
· 2026 Jun · PMID 42206899
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The spectroscopic observation of transient, low-valent copper intermediates under ambient conditions remains a formidable challenge due to their inherent high reactivity. Here, we report the spectroscopic observation and...The spectroscopic observation of transient, low-valent copper intermediates under ambient conditions remains a formidable challenge due to their inherent high reactivity. Here, we report the spectroscopic observation and dynamic stabilization of copper-radical species, achieved through the persistent radical effect (PRE) in a series of N-heterocyclic carbene copper(I) phenolates. Crucially, while these molecules exist as routine Cu(I) complexes with intact Cu-O bonds in the solid state, this homolytic behavior is activated upon dissolution in specific non-polar solvents. Electron paramagnetic resonance spectroscopy confirms the homolysis of Cu-O bonds, generating NHC-copper radicals and relatively persistent phenoxy radicals. The coexistence and interaction of these radicals were unambiguously evidenced by hyperfine splitting analysis and the detection of characteristic half-field signals, indicative of spin-coupled diradicals. The stability of these radical pairs is shown to depend critically on the matched reactivity between the copper-centered and organic radicals. This work establishes a PRE-driven strategy for characterizing and mitigating highly reactive copper-radical intermediates without the need for rigid ligand frameworks, providing new insights into copper radical chemistry and offering a practical approach for taming transient metal centers.
Tomalia NA, Rakova Y, Tubman AN
… +1 more, Matzger AJ
Dalton Trans
· 2026 Jun · PMID 42206852
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The temperature at which inorganic oxidizers evolve oxygen is a key operational constraint in applications ranging from energetic materials to chemical oxygen generators and life-support systems. However, commonly used c...The temperature at which inorganic oxidizers evolve oxygen is a key operational constraint in applications ranging from energetic materials to chemical oxygen generators and life-support systems. However, commonly used chlorates and perchlorates typically decompose at temperatures exceeding 400 °C, imposing limitations on efficiency, thermal management, and materials compatibility and motivating strategies for lower-temperature oxygen release without sacrificing yield. Here, porous Ni-based metal-organic frameworks catalyze LiClO decomposition, lowering oxygen evolution onset temperatures by up to 180 °C relative to pure LiClO while preserving >95 mol% O yield. Framework porosity enables oxidizer melt-infiltration and promotes intimate nanoscale oxidizer-catalyst contact, enhancing catalytic effectiveness relative to the most effective nonporous Ni catalyst identified through Ni-salt screening. This approach demonstrates how framework porosity can be leveraged to enhance oxidizer-catalyst interactions and improve catalytic efficiency in oxygen-generating systems through structural design rather than solely through metal identity or loading, enabling lower-temperature oxygen release without compromising oxygen yield.
Wu Z, Xiong C, Wang W
… +3 more, Yu Y, Du G, Chen N
Dalton Trans
· 2026 Jun · PMID 42206467
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Alkaline nickel-zinc (Ni-Zn) batteries are gaining attention as a promising energy storage solution, thanks to their remarkable specific power density, built-in safety features, and affordability. Nonetheless, zinc-based...Alkaline nickel-zinc (Ni-Zn) batteries are gaining attention as a promising energy storage solution, thanks to their remarkable specific power density, built-in safety features, and affordability. Nonetheless, zinc-based anodes face significant issues such as structural changes, dendrite formation, and electrochemical degradation, which greatly hinder the cycling stability and lifespan of these batteries. To overcome these challenges, this study introduces a metal doping approach, integrating a controlled amount of aluminum into zinc oxide (ZnO) solvothermal synthesis followed by calcination. This process yields a spherical composite of aluminum-doped ZnO (AZO) made up of porous nanosheets. The enhanced cycling stability of the AZO composite is attributed to the beneficial interplay between the optimized aluminum doping and its three-dimensional porous architecture. The addition of aluminum improves electronic conductivity, while the porous structure increases the number of reaction sites, facilitating better Zn deposition kinetics and minimizing electrode degradation. This composite demonstrates excellent cycling stability in nickel-zinc rechargeable batteries. This research paves the way for developing high-performance anode materials for Ni-Zn batteries, potentially expediting their commercialization.
Samsonov OV, Sharikov MI, Urintsev DI
… +5 more, Kulyabin PS, Goryunov GP, Uborsky DV, Canich JAM, Voskoboynikov AZ
Dalton Trans
· 2026 Jun · PMID 42206354
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Correction for 'Cyclopropyl isopropyl in zirconocenes: unexpected catalytic performance in propylene polymerization' by Oleg V. Samsonov , , 2026, https://doi.org/10.1039/d6dt00758a.Correction for 'Cyclopropyl isopropyl in zirconocenes: unexpected catalytic performance in propylene polymerization' by Oleg V. Samsonov , , 2026, https://doi.org/10.1039/d6dt00758a.
Almeida CMR, Selevich AF, Holz LIV
… +2 more, Loureiro FJA, Fagg DP
Dalton Trans
· 2026 Jun · PMID 42201769
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Two novel trivalent rare-earth mixed-anion phosphates, YHPO (YHPO) and ErHPO (EHPO), were synthesised using the thin layer technique (TLT) and processed into dense ceramic electrolytes the cold sintering process (CSP)....Two novel trivalent rare-earth mixed-anion phosphates, YHPO (YHPO) and ErHPO (EHPO), were synthesised using the thin layer technique (TLT) and processed into dense ceramic electrolytes the cold sintering process (CSP). Structural characterisation by powder X-ray diffraction confirmed tetragonal symmetry for both compositions, with slight variations in lattice parameters consistent with ionic radius differences between Y and Er. Chemical analysis and infrared spectroscopy verified the coexistence of orthophosphate (PO) and pyrophosphate (PO) groups in a 1 : 1 molar ratio, forming hydrogen-bonded networks relevant to proton transport. The cold-sintered pellets exhibited high relative densities (>88%) and preserved stoichiometry. Electrochemical impedance spectroscopy performed between 40 °C and 140 °C under controlled wet ( = 0.033 atm) and low humidity ( ∼ 10 atm) nitrogen atmospheres revealed humidity-dependent proton conduction. Under wet conditions, two transport regimes were identified: a low-temperature vehicular mechanism associated with surface-adsorbed water and a higher-temperature thermally activated regime consistent with Grotthuss-type proton hopping. EHPO exhibited superior conductivity, reaching 1.47 × 10 S cm at 140 °C, nearly one order of magnitude higher than YHPO. Under low humidity, both materials showed reduced conductivity and single Arrhenius-type behaviour with activation energies in the range of 50 kJ mol-60 kJ mol, indicating dominant structural proton diffusion. The enhanced performance of EHPO is attributed to its slightly more compact lattice, promoting favourable hydrogen-bond connectivity. These findings demonstrate the potential of trivalent rare-earth mixed phosphates as promising intermediate-temperature proton-conducting electrolytes.
Dalton Trans
· 2026 Jun · PMID 42189129
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High-entropy perovskite oxides are promising multifunctional electrocatalysts due to their complex defect structures derived from multi-elemental compositions. In this work, a Nd-based high-entropy perovskite, Nd(CoNiFeM...High-entropy perovskite oxides are promising multifunctional electrocatalysts due to their complex defect structures derived from multi-elemental compositions. In this work, a Nd-based high-entropy perovskite, Nd(CoNiFeMn)O (NCNFM), was synthesized using a sol-gel route to investigate the effect of B-site configurational disorder on oxygen non-stoichiometry and electrocatalytic behaviour. Structural characterization reveals the formation of a single-phase perovskite with randomly distributed transition-metal cations at the B-site. The NCNFM catalyst was deposited on nickel foam and evaluated for the oxygen and hydrogen evolution reactions (OER and HER), overall water splitting (OWS), and the methanol oxidation reaction (MOR). NCNFM demonstrated outstanding bifunctional activity, achieving overpotentials of 350 mV for the OER and 144 mV for the HER at 10 mA cm, with Tafel slopes of 91.2 and 105 mV dec, respectively, outperforming the other perovskite oxides. It obtained a cell voltage of 1.67 V at 10 mA cm and maintained stability for 72 hours in a self-supported two-electrode OWS system. NCNFM also showed superior MOR activity with a low onset potential of 1.467 V . RHE@100 mA cm, a low Tafel slope of 49 mV dec, and superior stability for at least 72 hours. The excellent catalytic behaviour of NCNFM is attributed to the synergistic effects among multiple B-site cations and the influence of configurational entropy, which enhance oxygen vacancy concentration and overall electrocatalytic activity.
Yadav S, Chourasia V, Ranjan P
… +3 more, De S, Saptal VB, Bera JK
Dalton Trans
· 2026 Jun · PMID 42188990
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The selective synthesis of secondary amines holds significant importance in organic chemistry, yet the development of an efficient catalytic route remains a challenge. Herein, we report the synthesis, characterization, a...The selective synthesis of secondary amines holds significant importance in organic chemistry, yet the development of an efficient catalytic route remains a challenge. Herein, we report the synthesis, characterization, and application of a well-defined ruthenium(II) catalyst (1) featuring a β-NH pyrazole moiety integrated within a naphthyridine-based ligand. This catalyst facilitates the deaminative self-coupling of primary amines to secondary amines through a borrowing-hydrogen strategy. Notably, the catalyst exhibits exceptional selectivity towards secondary amines, with no formation of overalkylated products or double dehydrogenated nitriles. Moreover, it demonstrates versatility across a wide range of benzylic, heterocyclic, and aliphatic long-chain primary amines. The metal-ligand cooperativity of the catalyst, attributed to the ruthenium metal center and pyrazole unit, enables the concurrent dehydrogenation of primary amines and hydrogenation of secondary imines, thus enhancing the selectivity towards secondary amines, confirmed by DFT calculations. Control experiments revealed the superior performance of the β-NH featuring ruthenium complex over its N-methylated counterpart, underscoring the metal-ligand cooperativity in facilitating the deaminative coupling reaction. This study presents a significant advancement in the catalytic synthesis of secondary amines, offering insights into the design of efficient catalytic systems for selective organic transformations.
Beliš M, Šrein J, Bhandary S
… +5 more, Premcheska S, Lederer M, Pompermayer Machado I, Kaczmarek AM, Van Hecke K
Dalton Trans
· 2026 Jun · PMID 42188428
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Dipyrido[3,2-:2',3'-]phenazine (dppz) is well known for its ability to interact with DNA and is ideally suited for sensitizing near-infrared (NIR)-emitting lanthanide ions such as Nd, Er and Yb. The combination of these...Dipyrido[3,2-:2',3'-]phenazine (dppz) is well known for its ability to interact with DNA and is ideally suited for sensitizing near-infrared (NIR)-emitting lanthanide ions such as Nd, Er and Yb. The combination of these properties gives perspective for the utilization of lanthanide complexes incorporating a dppz moiety for biomedical applications. Here, we present the synthesis of novel lanthanide complexes with an embedded dppz moiety [Ln(DO3A-dppz)] (Ln = all lanthanides except Pm; DO3A = 1,4,7,10-tetraazadodecane-1,4,7-triacetic acid) derived from clinically used [Ln(DOTA)] complexes (DOTA = 1,4,7,10-tetraazadodecane-1,4,7,10-tetraacetic acid). Structural analyses of all the complexes reveal interesting behavior, showing a share of isomers in the structures linked to lanthanide contraction and ionic radii. Photoluminescence studies provide excitation and emission spectra of the complexes with compatible central ions Nd, Er, Yb and Eu, along with decay times of the complexes with Yb and Eu. All complexes are weakly soluble in water with good stability in Tris-HCl buffer, and their affinity towards model calf-thymus DNA was tested using a SYBR Green I displacement assay. Overall, the obtained results are promising for the development of [Ln(DO3A-dppz)] complexes towards future applications in biomedical imaging.
Dalton Trans
· 2026 Jun · PMID 42187179
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Recent advances in achieving very high blocking temperatures in Dy(III)-based single-molecule magnets have brought the field closer to the long-standing goal of molecular alternatives to conventional magnets; however, th...Recent advances in achieving very high blocking temperatures in Dy(III)-based single-molecule magnets have brought the field closer to the long-standing goal of molecular alternatives to conventional magnets; however, the highest-performing systems are predominantly organometallic Dy(III) complexes, underscoring the need to integrate such systems into robust porous matrices for device-oriented applications. Here, we investigate the encapsulation of a dysprosium bis(amide)-alkene single-ion magnet [Dy{N(SiPr)[Si(Pr)C(CH)CHCH]}{N(SiPr)(SiPrEt)}] (1) within two porous hosts: an AFI-type zeolitic imidazolate framework [Zn(Im)] (F1) and a Cd-based MOF [Cd(L)(bpy)] (F2). As 1 is cationic, the influence of the counter-anion under confinement was explicitly examined. Encapsulation with chloride in the Cd-MOF induces compression of the N-Dy-N angle and enhances transverse crystal-field contributions, reducing the calculated barrier to = 1250.7 cm from 1528 cm. As the counter-anions are also anchored to the framework by non-covalent interactions, we have tested the stability of the guest molecule using molecular dynamics simulations. This study reveals that there is a strong driving force for the Cl ions to migrate within the pore and coordinate with the Dy centre, reducing the SIM performance. A relatively bulkier anion, such as a fluorinated aluminate model anion, Al(OCF), mitigates this problem and restores axial symmetry. Density functional theory calculations reveal favourable host-guest binding (-357 kJ mol for 1Cl@F1 and -246.2 kJ mol for 1Al(OCF3)4F2). Noncovalent interaction analysis confirms extensive pore-guest contacts, and comparison of binding energies computed with and without the D3 correction indicates that dispersion accounts for ∼35% of the stabilisation in 1Cl@F1 and ∼70% in 1Al(OCF3)4@F2. CASSCF/RASSI-SO calculations demonstrate that the magnetic anisotropy barrier is largely retained upon encapsulation ( = 1528 cm for 1, 1507.7 cm for 1Cl@F1, and 1511 cm for 1Al(OCF3)4@F2). The combination of strong host-guest binding and preservation of the magnetic barrier through judicious counteranion and host selection highlights encapsulation as a promising strategy for future applications of this class of molecules.
Bottari G, Moreno JJ, Salazar V
… +7 more, Campos J, Mereiter K, Rendón N, Cerón JE, López-Serrano J, Paneque M, Santos LL
Dalton Trans
· 2026 Jun · PMID 42187153
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The reactions between the Rh(I) ethylene complex TpRh(CH) (1; Tp = hydrotris(pyrazolyl)borate), and the alkynes di--butylacetylene dicarboxylate (DTBAD), acetylene, phenylacetylene, and methyl propiolate (MP) have been s...The reactions between the Rh(I) ethylene complex TpRh(CH) (1; Tp = hydrotris(pyrazolyl)borate), and the alkynes di--butylacetylene dicarboxylate (DTBAD), acetylene, phenylacetylene, and methyl propiolate (MP) have been studied, and the results compared with those obtained previously for dimethylacetylene dicarboxylate (DMAD). Electron withdrawing groups (DTBAD) at both termini of the triple bond stabilize η-diene-Rh(I) species, while terminal alkynes (acetylene, phenylacetylene) easily lead to η-allyl-Rh(III) species. The terminal alkyne methyl propiolate, with only one electron withdrawing substituent, exhibits an intermediate behavior, forming both η-diene-Rh(I) and η-allyl-Rh(III) species. Two types of intermediate octahedral TpRh(III) rhodacycles have been detected and characterized by NMR. Mechanistic investigations by DFT are also in agreement with the intermediate role of these types of species, which form oxidative coupling of compounds of type [TpRh(CH)(CR)] and [TpRh(CR)]. Ligand exchange reactions to form these species from 1 are instrumental in the outcome of the reactions.
Dalton Trans
· 2026 Jun · PMID 42187147
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Phosphates play pivotal roles in numerous critical biological processes. They encompass crucial biomolecules, such as phosphorylated amino acids, nucleotide phosphates, phosphoesters, phosphorylated proteins, and phospho...Phosphates play pivotal roles in numerous critical biological processes. They encompass crucial biomolecules, such as phosphorylated amino acids, nucleotide phosphates, phosphoesters, phosphorylated proteins, and phospholipids, which utilize inorganic phosphates (Pi) during their biosynthesis. Dysregulation of the phosphate levels has been implicated in various chronic and acute renal diseases. Therefore, the precise detection and quantification of phosphates hold paramount importance for disease diagnosis, drug development, and physiological assessment. Luminescent lanthanide-based sensors have emerged as a promising avenue for physiological phosphates due to their unique photophysical properties, originating from f-f transitions, and favourable binding thermodynamics strong ionic interactions, thereby surpassing their traditional organic counterparts and transition-metal complexes. This study introduces (Eu(TFNB)(L))(OTf) [Eu.1] as a luminescent Eu(III) probe designed for the detection of inorganic phosphate (Pi) displacement of the weaker binding neutral ligand (L) by the stronger binding phosphate anion. The dual-sensitized Eu(III) probe contains a neutral nitrogen-rich Schiff base (L) (,'-cyclohexanediyl-bis-2-pyridinyl-methanamine) and two anionic β-diketonate (trifluoro-naphthyl-butanedionate, TFNB) units. The Eu.1 probe was extensively characterized using various physicochemical and spectroscopic techniques to establish its molecular structure, solid and solution stability, and photoluminescence behavior. The characteristic red luminescence, originating from the D → F f-f transitions in the Eu.1 probe, was utilized as the optical signal to detect inorganic phosphates along with other interfering anions quantitative luminescence titrations. Detailed binding studies suggest that significant luminescence quenching of Eu.1 with HPO operates a competitive ligand dissociative mechanism due to the thermodynamically favorable strong hard-hard electrostatic interactions between the Eu(III) ion and HPO, enabling rapid and selective phosphate sensing at nanomolar (nM) concentrations. The comprehensive spectroscopic methods confirm the binding stoichiometry, affinity, selectivity and high sensitivity of the Eu.1 probe for inorganic phosphates in solution.
Zhao Y, Zhang J, Li S
… +6 more, Schwedtmann K, Wenzel M, Doert T, Xing H, Yang L, Weigand JJ
Dalton Trans
· 2026 Jun · PMID 42187113
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Synergistic liquid-liquid extraction (LLE) of Li commonly relies on β-diketonates in combination with neutral phosphine oxides such as tri--octylphosphine oxide (TOPO), yet the co-ligand is typically treated as an empiri...Synergistic liquid-liquid extraction (LLE) of Li commonly relies on β-diketonates in combination with neutral phosphine oxides such as tri--octylphosphine oxide (TOPO), yet the co-ligand is typically treated as an empirical additive rather than a design element. Here we show that commercially available diphosphine dioxides, featuring a preorganised PO⋯PO donor set and a spacer-defined bite, act as powerful co-ligands for Li extraction with 3-benzoyl-1,1,1-trifluoroacetone (HBTA) under mild pH conditions. Compared to TOPO, the best-performing PO⋯PO co-ligand enhances Li transfer while suppressing Na/K co-extraction, consistent with altered solution speciation and stoichiometry. These results establish a chelating co-ligand (PO⋯PO) as a simple, modular strategy to control synergy in Li extraction systems based on classical CO⋯CO extractants such as HBTA.
Palii A, Belonovich V, Korchagin D
… +2 more, Aldoshin S, Tsukerblat B
Dalton Trans
· 2026 Jun · PMID 42187103
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Based on the theoretical framework recently developed by some of us, we predict and justify the possibility of a nonequilibrium magnetic cooling effect in the Mn family of clusters by considering a monocrystalline sample...Based on the theoretical framework recently developed by some of us, we predict and justify the possibility of a nonequilibrium magnetic cooling effect in the Mn family of clusters by considering a monocrystalline sample of the prototypical single-molecule magnet MnAc as a representative example. In contrast to the quasi-static processes underlying the conventional magnetocaloric effect (MCE), we address a dynamic regime involving sudden magnetic field quenching. The proposed cooling mechanism is determined by the relaxation kinetics arising after a sudden change in the spin Hamiltonian that generates a nonequilibrium population distribution within the spin subsystem and therefore does not rely on the standard equilibrium entropy cycles. During the subsequent restoration of thermal equilibrium, heat is redistributed between the phonon bath and the spin degrees of freedom. Under appropriate conditions, this relaxation-driven process results in cooling of the lattice. The central result is that the strong easy-axis magnetic anisotropy associated with a significant magnetization reversal barrier, features typically considered detrimental to conventional magnetocaloric cooling, becomes advantageous in the nonequilibrium regime. These properties enhance both the magnitude of the cooling effect and the practical feasibility of the sudden-quench approach. This study therefore broadens the potential cryogenic applicability of single-molecule magnets by identifying a cooling mechanism that operates precisely in the parameter range where classical magnetocaloric approaches are least efficient.
Costa AR, de Oliveira LP, Palmeira-Mello MV
… +16 more, de Araujo-Neto JH, Lima MA, Moraes CA, de Farias RL, Demidoff FC, Neto CD, Cominetti MR, de Melo MRS, Nicolella HD, Mendes Abe SH, Fonseca EKB, Arruda MAZ, Ellena JA, Tavares DC, Rocha FV, Batista AA
Dalton Trans
· 2026 Jun · PMID 42186346
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Breast cancer (BC) is one of the most challenging types of cancer in women. Triple-negative breast cancer (TNBC) is an aggressive and rapidly progressive subtype that lacks targeted therapies, relying primarily on chemot...Breast cancer (BC) is one of the most challenging types of cancer in women. Triple-negative breast cancer (TNBC) is an aggressive and rapidly progressive subtype that lacks targeted therapies, relying primarily on chemotherapy. Given the limited treatment options for TNBC, novel therapeutic strategies are needed to address this disease. In this context, here we report the synthesis and characterization of four ruthenium(II) complexes containing naphthoquinone derivatives as ligands: [Ru(NQ1)(bipy)(dppen)]PF (Ru1), [Ru(NQ2)(bipy)(dppen)]PF (Ru2), [Ru(NQ1)(bipy)(DPEphos)]PF (Ru3), and [Ru(NQ2)(bipy)(DPEphos)]PF (Ru4), where bipy = 2,2'-bipyridine, dppen = 1,2-bis(diphenylphosphino)ethylene, DPEphos = bis[(2-diphenylphosphino)phenyl]ether, and NQ1 and NQ2 = deprotonated lawsone and lapachol, respectively. Mass spectrometry and elemental analyses were used to confirm the purity of the complexes. assays showed that Ru1-Ru4 were cytotoxic against MDA-MB-231 and MCF-7 (breast cancer cell lines) and A549 (lung cell line). The compounds exhibited lower IC values than cisplatin, used as a control. Ru4 was the most promising compound, with the highest selectivity index for the triple-negative breast cancer cell line (SI = 25.5). Furthermore, this complex inhibited colony formation, induced apoptosis, and affected the cell cycle in these cancer cells. Western blot analysis showed increased cleaved caspase-3 expression, corroborating the apoptotic mechanism observed by flow cytometry. Furthermore, cell uptake studies showed that ruthenium was found at the intracellular level after treatment with the MDA-MB-231 cell line. DNA-binding studies revealed an interaction between Ru1-Ru4 and Ct-DNA the minor groove pocket, as confirmed by molecular docking. Overall, our results suggest [Ru(NQ2)(bipy)(DPEphos)]PF (Ru4) to be a promising cytotoxic agent against breast cancer.
Guk DA, Karetnikov GL, Moiseeva AA
… +10 more, Ipatova DA, Alekseechkina UG, Skvortsov DA, Grishin YK, Tafeenko VA, Lyssenko KA, Khan II, Pokrovsky VS, Pergushov VI, Beloglazkina EK
Dalton Trans
· 2026 Jun · PMID 42171449
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A synthetic approach to the first hybride triazolyl-pyridyl-imidazolone ligands with redox-active auxiliary groups was developed. These tridentate ligands may be used to obtain copper coordination compounds of two struct...A synthetic approach to the first hybride triazolyl-pyridyl-imidazolone ligands with redox-active auxiliary groups was developed. These tridentate ligands may be used to obtain copper coordination compounds of two structural types, differing in the oxidation state of the copper ion and the geometry of its environment. These complexes were successifully synthesised and characterized by NMR, CV, RDE, HRMS, EPR, and XRD data. All coordination compounds exhibited cytotoxic activity against the MCF-7 and A549 tumor cell lines, exceeding significantly the IC50 of the free ligands. The two most promising complexes, 11c and 15c, demonstrated cytotoxicity at low micromolar concentrations, selectivity better than cisplatin, and inhibition of tumor growth . The mechanism of cytotoxic action of these complexes is most likely associated with oxidative cleavage of DNA under redox reactions involving metal ions in coordination compounds.
Das S, Das Pattanayak P, Mohapatra D
… +1 more, Dinda R
Dalton Trans
· 2026 Jun · PMID 42171394
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Vanadium, a metal essential for biological processes, is well known in anticancer research due to its strong ability to combat tumours. Their coordination flexibility with a wide range of oxidation states and different b...Vanadium, a metal essential for biological processes, is well known in anticancer research due to its strong ability to combat tumours. Their coordination flexibility with a wide range of oxidation states and different bioactive ligands offer structural versatility, making it a prominent focus in current medicinal chemistry. Many reviews discuss vanadium complexes (VCs) and their potential as anticancer agents, but none focus specifically on mixed-ligand oxidovanadium complexes (MLOVCs) as potential metallodrugs or their role in anticancer research. This review summarises recent advancements in synthesising MLOVCs with various ligands and their corresponding oxidation states under diverse reaction conditions. It organises the studied complexes based on the type of ligands they contain and their oxidation levels, highlighting how using biologically relevant ligand/co-ligands helps improve their stability, solubility, ability to enter cells, and their potential as an anticancer agent. The analysis aims to guide researchers in creating more effective and selective vanadium-based anticancer metallodrugs, advancing the fight against cancer.