Dalton Trans [JOURNAL]
Sun
200 papers
Ligand-dependent electronic structure, bonding, and optical properties of M(L)(CO) complexes (L = acac, Cp, Cp; M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt): a systematic DFT/TD-DFT study.
Thomas R, Khairbek AA, Abdullah Alzahrani AY … +2 more , Saleh DI, Mahmoud SF
Dalton Trans · 2026 Jul · PMID 42381533 · Publisher ↗
Transition-metal carbonyl complexes display rich electronic structures governed by the interplay of metal d orbitals and ligand π systems. Here, a systematic DFT and TD-DFT study was performed on 27 complexes of the type...
Transition-metal carbonyl complexes display rich electronic structures governed by the interplay of metal d orbitals and ligand π systems. Here, a systematic DFT and TD-DFT study was performed on 27 complexes of the type M(L)(CO) (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; L = acac, Cp, Cp*). Geometry optimizations, Mayer bond orders, ADCH charges, frontier molecular orbital energies, and global reactivity descriptors were evaluated at the MN12-L/def2-TZVP level. Scalar relativistic effects for the 4d (Ru, Rh, Pd) and 5d (Os, Ir, Pt) metals are implicitly included through the Stuttgart-Cologne small-core relativistic effective core potentials (ECP28MWB and ECP60MWB) that accompany def2-TZVP. Electronic absorption spectra were simulated in cyclohexane TD-DFT with Gaussian convolution ( = 20 nm) to obtain realistic values. The results reveal a recurrent ligand-dependent pattern: more ionic acac ligands consistently induce a more positive metal charge, longer M-C(CO) bond lengths (1.77-1.99 Å) and lower Mayer bond orders relative to those of the covalent Cp and Cp* analogs. The HOMO-LUMO gap is wider for acac than for the corresponding Cp/Cp* derivative in seven of the nine metals studied; the three d M(I) cases (Co, Rh, Ir) are clear exceptions in which Cp/Cp* widens the gap further owing to strong covalent donation. The computed MLCT energies, ADCH-charge orderings and CO stretching frequencies for the Ir benchmark series are in quantitative agreement with recently reported HERFD-XAS, VtC-RIXS and infrared data. This work provides a comprehensive understanding of how ancillary-ligand ionicity modulates the metal-ligand bonding, charge distribution, and optical properties of organometallic carbonyl complexes.
Metal oxide hollow heterojunctions derived from bimetal-organic frameworks for efficient urea photosynthesis.
Xiao S, Li B, Liang Z … +2 more , Zheng W, Yuan W
Dalton Trans · 2026 Jul · PMID 42381521 · Publisher ↗
As urea is an important chemical in agriculture, the green synthesis of urea has attracted widespread attention. However, developing simple and green strategies for urea synthesis remains challenging. In this study, we d...
As urea is an important chemical in agriculture, the green synthesis of urea has attracted widespread attention. However, developing simple and green strategies for urea synthesis remains challenging. In this study, we developed a novel metal oxide hollow heterojunction for efficient photocatalytic urea synthesis. By calcining a bimetallic MUV-10 MOF precursor in an air atmosphere, the TiO/MnO (denoted as TMO) metal oxide hollow heterojunction was successfully prepared, while the octahedral structure was well preserved. Among these catalysts, the bimetallic oxide TMO-8 exhibits the highest light-harvesting capability and photogenerated carrier separation efficiency, enabling efficient photocatalytic urea synthesis from CO and NH. Under visible light irradiation, the TMO-8 hollow heterojunction achieved a high urea production rate of 93 µmol g h, which surpasses those of the state-of-the-art photocatalysts. This study provides a new strategy for designing efficient heterojunction photocatalysts and offers an efficient pathway for artificial photosynthetic urea synthesis under mild conditions.
Ce(III) containing tricobalt-substituted silico-tungstate [CeCoSiWO(NO)(OH)(HO)]: a versatile nano-cluster with a multitude of applications.
Shivani, Das V, Ul Haq A … +9 more , Prandiyal S, Alam A, Teillout AL, de Oliveira P, Kant A, Himani, Mishra D, Blacque O, Hussain F
Dalton Trans · 2026 Jul · PMID 42381518 · Publisher ↗
In this work, we report a structurally distinct cerium-containing tricobalt-substituted Keggin-type silico-tungstate [CeCoSiWO(NO)(OH)(HO)]. In addition to the Ce-based complex (2a), we have also isolated structures incl...
In this work, we report a structurally distinct cerium-containing tricobalt-substituted Keggin-type silico-tungstate [CeCoSiWO(NO)(OH)(HO)]. In addition to the Ce-based complex (2a), we have also isolated structures including other early lanthanoids consisting of La (1a), Pr (3a), and Nd (4a). The polyoxotungstates were synthesised by reacting Na[A-α-SiWO]·16HO with Ln(NO)·HO in potassium chloride at 80 °C for 1 h. Later, the solution was left to evaporate in a cool, dark place, and undisturbed. The solid crystalline material polytungstates were further structurally characterised by SC-XRD, FT-IR, TGA, UV/Vis spectroscopy and electrochemistry. The single-crystal X-ray diffraction analysis and FT-IR spectra suggest that the compounds are isostructural. The synthesised polyanionic compounds exhibited significant catalytic activity in two distinct applications: Dye degradation and the Hydrogen Evolution Reaction (HER). Furthermore, the anti-cancer activity was also assessed against human alveolar cells.
Physicochemical properties and biological activity of heteroleptic cyclometalated Rh(III) complexes. A comparative analysis with Ir(III) analogues based on 3,5-dimethyl-1-phenyl-1-pyrazole and auxiliary ligands.
Okła K, Maciejewska N, Sitkowski J … +5 more , Kamecka A, Kazimierczuk K, Zienkiewicz-Machnik M, Barszcz B, Masternak J
Dalton Trans · 2026 Jun · PMID 42371010 · Publisher ↗
To directly probe the role of the metal centre in cyclometalated anticancer agents, we developed a new series of heteroleptic Rh(III) complexes as rhodium congeners of our previously reported Ir(III) complexes based on t...
To directly probe the role of the metal centre in cyclometalated anticancer agents, we developed a new series of heteroleptic Rh(III) complexes as rhodium congeners of our previously reported Ir(III) complexes based on the same C,N-donor ligand framework. Such a comparative insight will allow us to take a broader look at the mechanism of action of the complexes under investigation as potential chemotherapeutic agents. Three novel cyclometalated Rh(III) compounds containing 3,5-dimethyl-1-phenyl-1-pyrazole (Hdmppz) and the N,N-donor ligands 2-di(pyridyl)ketone (PyCO), 2,2-biimidazole (Hbiim), and 2-(2-pyridyl)benzimidazole (PyBIm) were synthesized: [Rh(dmppz)(PyCO)]PF (1), [Rh(dmppz)(Hbiim)]PF·HO (2), and [Rh(dmppz)(PyBIm)]PF·HO (3). This matched Rh(III)/Ir(III) design enables a rare head-to-head comparison in which the ligand environment is retained and the central ion is the key variable. The complexes were comprehensively characterised by SC-X-ray diffraction, FTIR, elemental analysis, ESI-MS, UV-Vis, PL, and H, C and N NMR spectroscopy. The biological evaluation showed that the new Rh(III) complexes display pronounced antiproliferative activity against MCF-7, K-562 and CCRF-CEM cancer cell lines, with IC values determined together with those for the normal MRC-5 cell line. To elucidate their mode of action, interactions with biologically relevant targets, namely DNA and HSA, were studied by UV-Vis and CD spectroscopy as well as molecular docking. Their redox reactivity toward NADH and GSH was also examined by UV-Vis. In addition, intracellular ROS generation, cell-cycle perturbation, apoptosis induction and confocal microscopy imaging were investigated. Most importantly, comparison with the previously reported Ir(III) analogues demonstrates that replacing Ir(III) with Rh(III) within the same cyclometalated scaffold significantly affects the biological profile of the complexes. The results indicate that DNA interaction is largely governed by the ligand framework, whereas modulation of cellular redox processes depends more strongly on the nature of the metal centre. These findings identify the new Rh(III) complexes as promising multitarget cytotoxic agents and establish direct Rh(III)/Ir(III) comparison as a useful strategy for the rational design of new metallodrugs.
Light-responsive spin-crossover iron(II) complexes with azo-pyridyl-benzimidazole ligands for molecular thin films.
Čierny O, Šagátová A, Orvoš J … +12 more , Pavlik J, Moncoľ J, Nemec I, Halahovets Y, Hofbauerová M, Šiffalovič P, Mičušík M, Meunier JF, Brachňaková B, Fischer R, Michalík M, Šalitroš I
Dalton Trans · 2026 Jun · PMID 42370952 · Publisher ↗
We report the synthesis, structural characterization, and multifunctional properties of three new iron(II) spin-crossover (SCO) complexes based on the azo-functionalized ligand 2-{4-[-phenyldiazenyl]-pyridine-2-yl}-1-ben...
We report the synthesis, structural characterization, and multifunctional properties of three new iron(II) spin-crossover (SCO) complexes based on the azo-functionalized ligand 2-{4-[-phenyldiazenyl]-pyridine-2-yl}-1-benzimidazole (L): [Fe(L)](ClO)·CHO (1), ([Fe(L)](CFSO)) (2) and [Fe(L)](BF)·CHO (3). Single-crystal X-ray diffraction reveals isostructural [Fe(L)] cations with octahedral {FeN} coordination environments, adopting a low-spin state at 100 K. Temperature-dependent magnetic measurements and Mössbauer spectroscopy demonstrate gradual thermal SCO behaviour, with transition temperatures tuneable by solvation and counter-anion effects. All three complexes exhibit light-induced excited spin-state trapping (LIESST) at low temperatures, with photo-conversion yields reaching up to 63%. The photoisomerization of the azo unit was investigated in solution and in solid thin films, revealing efficient → switching in solution and a remarkably stable form in the solid state under ambient conditions. Multireference computational studies supported by TDDFT calculations provide insight into the photoswitching mechanism and indicate possible triplet sensitisation of the azo bond located in the vicinity of the high-spin Fe(II) centre. Furthermore, the successful fabrication of Langmuir-Blodgett monolayer and multilayer films was demonstrated, with AFM and XPS confirming molecular-level film organization and preservation of metal-ligand coordination at the surface. Together, these results establish azo-functionalized pyridyl-benzimidazole ligands as a versatile platform for integrating thermal SCO, light responsiveness, and surface assembly, offering promising prospects for multifunctional molecular switches and surface-integrated photomagnetic devices.
Polymorphic LiZnSbO with orthorhombic and monoclinic phases for the efficient photocatalytic degradation of RhB and tetracycline in wastewater.
Yao G, Jia Q, Pan F … +4 more , Quan L, Pei C, Song S, Jia Y
Dalton Trans · 2026 Jun · PMID 42370949 · Publisher ↗
In this work, polymorphic LiZnSbO powders have been synthesized the solid-state reaction route, and their photocatalytic performances have been investigated under ultraviolet (UV) light illumination. XRD analysis disclo...
In this work, polymorphic LiZnSbO powders have been synthesized the solid-state reaction route, and their photocatalytic performances have been investigated under ultraviolet (UV) light illumination. XRD analysis discloses that a phase transition from the orthorhombic (α-LiZnSbO) to monoclinic (β-LiZnSbO) crystal system occurs while sintering above 1100 °C. Under UV light illumination for 90 min, α-LiZnSbO exhibits a higher degradation ratio (92%) for RhB (5 mg L) compared with that for β-LiZnSbO (27%), which is due to its relatively high crystal symmetry and surface area and thus effectively increasing the carrier mobility. The α-LiZnSbO catalyst also displays remarkable recyclability even after four successive cycles. On the basis of the scavenging and electron paramagnetic resonance (EPR) trapping measurement results, the confirmed active radicals are ˙OH and ˙O in the photocatalytic reaction. The degradation routes of RhB have been elucidated according to the intermediates detected. Besides RhB, tetracycline (TC) can also be efficiently degraded by α-LiZnSbO.
Homoleptic nickel(II) and cobalt(II) complexes of ,'-dialkyl-β-dialdiminato ligands as potential chemical vapor deposition precursors.
Schmit CE, Girolami GS
Dalton Trans · 2026 Jun · PMID 42370938 · Publisher ↗
A series of volatile cobalt(II) and nickel(II) ,'-dialkyl-bis(β-dialdiminato) complexes of stoichiometry M[RN(CH)NR] (where R = methyl, ethyl, iso-propyl, or -butyl) have been prepared and characterized. NMR, IR, and UV-...
A series of volatile cobalt(II) and nickel(II) ,'-dialkyl-bis(β-dialdiminato) complexes of stoichiometry M[RN(CH)NR] (where R = methyl, ethyl, iso-propyl, or -butyl) have been prepared and characterized. NMR, IR, and UV-vis spectra are reported, along with their magnetic properties and crystal structures. IR and crystallographic data support the conclusion that all these complexes contain divalent metal ions and closed-shell monoanionic ligands. NMR studies indicate that some spin density is delocalized directly into the π-orbitals of the β-dialdiminate ligand, as seen in other ,'-diaryl and β-diketiminato compounds of cobalt(II) and nickel(II), and magnetic measurements afford magnetic moments that are larger than the spin-only values owing to orbital contributions to the moments. In the UV-Vis spectra, the higher energy spin-allowed d-d transition can be observed in the visible (or near visible) region. Overall, these new cobalt(II) and nickel(II) compounds are similar to their ,'-diaryl and β-diketiminato analogues, but have lower molecular masses and thus are more volatile, making them potentially useful precursors for the chemical vapor deposition (CVD) of cobalt- or nickel-containing films.
CuI passivation layer for stabilizing BiI-sensitized QDSSCs: long-term performance stability assessment.
Saleem S, Hu TY, Hui K … +2 more , Wang YF, Zeng JH
Dalton Trans · 2026 Jun · PMID 42370631 · Publisher ↗
Poor performance stability in quantum dot-sensitized solar cells (QDSSCs), mainly arising from electrolyte-induced degradation at the ETM/QD interface, has not been widely investigated. We addressed this problem by using...
Poor performance stability in quantum dot-sensitized solar cells (QDSSCs), mainly arising from electrolyte-induced degradation at the ETM/QD interface, has not been widely investigated. We addressed this problem by using PbI and CuI passivation layers for BiI-sensitized QD-sensitized solar cells with solid-state electrolyte species due to their higher conduction band and valence band than that of the BiI sensitizer and TiO electron transport material (ETM), and good thermal stability. We improved the performance stability of BiI-sensitized solar cells over 30 days using the CuI passivation layer and reached a maximum efficiency of 6.55% (degraded to 4.82%, which was 73.58% of the initial day), which was superior to the PbI-passivated device. The CuI passivation layer produced the least defective surface of the photoanode (as confirmed by field emission scanning electron microscopy), which restricted direct contact between the ETM and electrolyte, thereby reducing leakage of the electrolyte. As a result, the sensitizer did not undergo degradation under prolonged illumination. Furthermore, - traces under dark conditions confirmed a very small leakage current, which was a sign of better performance stability of the device. These findings suggested that the CuI passivation layer offered good performance stability of the BiI-sensitized QDSSC as compared with that of the PbI-passivated device.
Zwitterionic-to-cationic ruthenium carbazole complexes: structure and selective hydroboration of quinolines and pyridines.
Sanchez-Lecuona G, Wells GM, Gyton MR … +4 more , Zamora-Moreno J, Duckett SB, Webster CE, Montiel-Palma V
Dalton Trans · 2026 Jun · PMID 42370607 · Publisher ↗
We report the synthesis of the Ru(II) zwitterionic complexes [MeRu(η-carbazole--EMeCl)(PPh)] (E = Al, Ru-1; Ga, Ru-2) a one-pot reaction of RuCl(PPh) with carbazole in the presence of excess group 13 trialkyl reagents (...
We report the synthesis of the Ru(II) zwitterionic complexes [MeRu(η-carbazole--EMeCl)(PPh)] (E = Al, Ru-1; Ga, Ru-2) a one-pot reaction of RuCl(PPh) with carbazole in the presence of excess group 13 trialkyl reagents (AlMe or GaMe). Structural characterization confirms η-coordination of ruthenium to a single fused aryl ring of the carbazole framework. The zwitterionic character of Ru-1 and Ru-2 results from deprotonation of the carbazole N-H bond to form an anionic amido fragment coordinated to a group 13 center, while the cationic Ru(II) center is supported by two phosphines, a methyl ligand, and an η-bound carbazole-derived ligand. Treatment of Ru-1 or Ru-2 with Brookhart's acid [H(OEt)][BArF4] reprotonates the amido nitrogen to afford the complex cation [MeRu(η-carbazole)(PPh)] (Ru-3). While the zwitterionic complexes Ru-1 and Ru-2 show modest catalytic activity, protonation generates the highly active ion pair Ru-3, which exhibits superior activity and regioselectivity in the hydroboration of N-heterocycles, enabling either 1,4-reduction of pyridines or 1,2-reduction of quinolines under mild, solvent-free conditions without additional additives. Turnover numbers (TONs) of up to 874 for quinoline and 1000 for pyridine are achieved in gram scale reactions. These values compare favorably with those reported for related Ru, Rh, and Ni systems. Overall, this work provides a rare example of a group 13-stabilized zwitterionic ruthenium-arene system derived from carbazole activation and demonstrates its conversion into a highly active cationic catalyst, expanding the scope of ruthenium-arene chemistry for the selective functionalization of N-heterocycles.
GdOCl-modified polymeric carbon nitride heterojunction for one-photon excitation efficiently driven photocatalytic hydrogen production.
Habib S, Li JH, Habib A … +4 more , Chen S, Ding HY, Tian RX, Xu AW
Dalton Trans · 2026 Jun · PMID 42370511 · Publisher ↗
Visible light driven photocatalytic hydrogen evolution using sacrificial agents is a promising route for solar to chemical energy conversion. However, achieving efficient charge separation and migration in heterogeneous...
Visible light driven photocatalytic hydrogen evolution using sacrificial agents is a promising route for solar to chemical energy conversion. However, achieving efficient charge separation and migration in heterogeneous semiconductor photocatalysts through a one-photon excitation process remains challenging. In this work, we report a one-photon excitation approach by integrating polymeric carbon nitride (PCN) with gadolinium oxychloride (GdOCl) by a molten salt method for photocatalytic hydrogen evolution over PCN/GdOCl photocatalysts. Notably, the optimized PCN/GdOCl-1.5 exhibits an impressive H performance with a yield of 86.38 μmol h, surpassing bare PCN by a factor of 4.7. Additionally, PCN/GdOCl-1.5 showcases enhanced photocatalytic H production with an apparent quantum efficiency (AQE) of 6.17% under monochromatic light at 420 nm. The improved separation of photogenerated charge carriers and reduced recombination rates in PCN/GdOCl-1.5 were evidenced by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS). In addition, the photocatalyst displays outstanding stability and retains its photocatalytic performance over five successive reaction cycles, thereby emphasizing the potential of PCN/GdOCl-1.5 for efficient and sustainable hydrogen evolution. The enhanced H evolution performance is attributed to visible light excitation of PCN, followed by GdOCl assisted interfacial charge regulation and built-in electric field (BIEF) driven charge carrier migration. This work provides insight into the design of PCN based heterojunction photocatalysts for sacrificial agent assisted photocatalytic hydrogen evolution.
Chalcogen bonding weakly coordinating anions - a solid state study on halidoselenium cations in an oxoanionic environment.
Langwald J, Burguera S, Frontera A … +1 more , Wickleder MS
Dalton Trans · 2026 Jun · PMID 42370399 · Publisher ↗
We present the crystal structure of selenoyl chloride, SeOCl, for the first time and show that it can be used for the subsequent synthesis of novel compounds with the [SeCl] cation, which we stabilized as disulfate [SO]...
We present the crystal structure of selenoyl chloride, SeOCl, for the first time and show that it can be used for the subsequent synthesis of novel compounds with the [SeCl] cation, which we stabilized as disulfate [SO] and chlorosulfate [ClSO] salts, respectively. Both, SeOCl as well as the [SeCl] salts show remarkable macromolecular arrangements and packing motifs in the solid state, so far not or only scarcely analyzed. Additionally, we report the stabilization of the dication [SeI] in the tetrasulfate salt [SeI][SO](SO). This marks the very first examples of the respective cations in an oxoanionic environment. All compounds show strong and directional non-covalent interactions, chalcogen bonding, as well as, to a lesser degree, halogen bonding (HaB). These interactions were investigated Density functional theory (DFT) investigations, molecular electrostatic potential (MEP) surface plots, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. Overall, this work demonstrates that, while coulombic forces are the primary drivers in these ionic systems, the directionality and specific orbital contributions of σ- and π-hole interactions are essential for fine-tuning the final supramolecular assemblies.
Crystal structures and luminescence properties of CaRESiON (RE = Y, La, and Ce) activated by Ce.
Kobayashi M, Yasunaga T, Nagahama C … +5 more , Fujii K, Yashima M, Osada M, Kato H, Kakihana M
Dalton Trans · 2026 Jun · PMID 42367180 · Publisher ↗
The discovery of new compounds expands the scope of materials chemistry. In this study, we report a new series of oxynitride compounds, CaRESiON (RE = Y, La, and Ce), and their crystal structures. The samples were synthe...
The discovery of new compounds expands the scope of materials chemistry. In this study, we report a new series of oxynitride compounds, CaRESiON (RE = Y, La, and Ce), and their crystal structures. The samples were synthesized by a solid-state reaction method under an inert atmosphere. Single-crystal X-ray diffraction analysis revealed that these compounds are isostructural and crystallize in the cubic space group 3̄. The structures contain four crystallographically distinct cation sites and unique isolated 12-membered ring units constructed from Si(O,N) tetrahedra. Ce-containing samples exhibit broad photoluminescence under ultraviolet excitation, and the emission colour changes from deep blue to bluish green with varying RE composition. Analysis of the emission spectra suggests that the luminescence originates from multiple crystallographic sites and exhibits thermal quenching behaviour. These results demonstrate that CaRESiON represents a new class of oxynitride phosphors with multi-site luminescence and tuneable emission properties.
Engineering the rhenium metalation of phenanthroline imino complexes for variable structure activity relationships.
Jacobs FJF, Fourie E, Brink A
Dalton Trans · 2026 Jun · PMID 42367032 · Publisher ↗
There are marked advantages for incorporating multiple metal atoms into a single entity specifically for theranostic and radiopharmaceutical development for the treatment and imaging of cancer. To this end, we have synth...
There are marked advantages for incorporating multiple metal atoms into a single entity specifically for theranostic and radiopharmaceutical development for the treatment and imaging of cancer. To this end, we have synthetically manipulated a series of rhenium tricarbonyl complexes based on a 1,10-phenanthroline imino bifunctional ligand system to allow for the formation of mononuclear, dinuclear and mixed di-metal rhenium tricarbonyl complexes. Thus, diverse protein bio-chemical interactions are in principle possible by harnessing the chemical versatility of the the phenanthroline scaffold together with strategic metal substitution to advance drug development. The structure-activity relationships for these complexes are described indicating covalent and non-covalent interactions which are explored through the lens of macromolecular interactions and metallo-inorganic drug design. Complex characterisation was conducted with IR, H and C NMR, EA and detailed structural investigations using SC-XRD. Hirshfeld surface analysis indicated that halogen, hydrogen and oxygen-based hydrogen interactions play dominant roles in crystal packing and are significant to consider for drug design. drug likeness analysis of the compounds using Swiss ADME had predicted good potential bioactivity. HeLa and MCF-7 cell SRB assay was used to identify the cytotoxic properties of the -tricarbonyl-(1,10-phenanthroline-,')-(bromido)-rhenium(I), -tricarbonyl-{2-([1,10-phenanthrolin-5-ylimino]methyl)phenol-,'}-(bromido)-rhenium(I), -tricarbonyl-{2-([1,10-phenanthrolin-5-ylimino]methyl)phenol-,'}-(chlorido)-rhenium(I), -{2-([1,10-phenanthrolin-5-ylimino]methyl)phenolato-,'}-(methanol)(bromido)-hexacarbonyl-di-rhenium(I), and -bis{2-([1,10-phenanthrolin-5-ylimino]methyl)phenol-,'}-hexacarbonyl-di-rhenium(I). Excellent activity was shown for the free ligand and 1,10-phenanthroline with IC values of 9 ± 3 μM, 11 ± 2 μM (HeLa) and 8 ± 2 μM, 6 ± 2 μM (MCF-7) respectively. Rhenium complexes showed IC values ranging between 15 ± 2 μM and 35 ± 2 μM against HeLa cells and between 68 ± 2 μM and >100 μM against MCF-7 cells. A correlation is observed between good to moderate cytotoxicity and a balanced spread of H-bond interactions showing amphiphilic character.
Solvent-directed assembly of Ln and Ln-Co complexes based on a pyridyl-triazolyl functionalized nitronyl nitroxide radical: reduction from NIT to IM and magnetic properties.
Xia CC, Li F, Wang ML … +2 more , Yan X, Wang WZ
Dalton Trans · 2026 Jun · PMID 42366954 · Publisher ↗
A pyridine-triazole functionalized nitronyl nitroxide radical ligand NIT-4trz-3Py (NIT-4trz-3Py = 3-(4-(1-triazole)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was designed to construct a series of lanthani...
A pyridine-triazole functionalized nitronyl nitroxide radical ligand NIT-4trz-3Py (NIT-4trz-3Py = 3-(4-(1-triazole)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was designed to construct a series of lanthanide and Ln-Co magnetic complexes through solvent-regulated assembly. In total, seven complexes were successfully synthesized and structurally characterized: three dinuclear cyclic complexes [Ln(hfac)(NIT-4trz-3Py)] (Ln = Gd (1Gd), Tb (2Tb) and Dy (3Dy), hfac = hexafluoroacetylacetonate), two one-dimensional lanthanide chains [Ln(hfac)(NIT-4trz-3Py)] (Ln = Dy (4Dy) and Yb (5Yb)), and two Ln-Co heterometallic chains [LnCo(hfac)(IM-4trz-3Py)] (Ln = Dy (6DyCo), and Yb (7YbCo), IM-4trz-3Py = 3-(4-(1-triazole)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl). The cyclic and chain-like lanthanide assemblies were harvested from -heptane/dichloromethane mixed solvent and toluene, respectively, wherein lanthanide ions are interconnected in a head-to-head mode by intact NIT radicals. An unanticipated reduction of NIT to IM radical occurred during the crystallization of Ln-Co chains. Differently, Ln ions in heterometallic chains are linked in a head-to-tail fashion IM radicals, and Co ions are chelated between pyridine and triazole nitrogen sites. Slow relaxation of the magnetization can be observed under a zero dc field for complex 4Dy, while complexes 2Tb, 5Yb, 6DyCo, and 7YbCo reveal the field-induced slow magnetic relaxation behavior under an applied dc field. In the fluorescence spectra, complex 2Tb was found to exhibit four characteristic emission peaks of the Tb ion. This work presents unambiguous solvent-dependent structural diversity of nitroxide-based complexes, providing reliable insights for the rational design and controlled fabrication of low-dimensional molecular magnetic materials.
Oxygen vacancy-assisted 3DOM TiO-ZnCdS heterojunctions for enhanced photocatalytic hydrogen production.
Li H, Zhao ZL, Chen J … +9 more , Wang LD, Rong Y, Lyu JM, Liu J, Hu ZY, Mohamed HSH, Chen LH, Li Y, Su BL
Dalton Trans · 2026 Jun · PMID 42366936 · Publisher ↗
Photocatalytic hydrogen production is a promising strategy for alleviating the energy and environment crises. However, its practical application is still severely limited by insufficient visible-light utilization, the ra...
Photocatalytic hydrogen production is a promising strategy for alleviating the energy and environment crises. However, its practical application is still severely limited by insufficient visible-light utilization, the rapid recombination of photogenerated charge carriers and slow surface reaction efficiency. To address these issues, a series of oxygen vacancy-assisted three-dimensionally ordered macroporous (3DOM) TiO-ZnCdS composite photocatalysts are designed for enhanced hydrogen production. In this heterojunction structure, the interfaces between TiO and ZnCdS are largely decreased the formation process to promote the transfer of photogenerated charge carriers. In particular, the extra-generated oxygen vacancies regulate the band structure of the composite photocatalyst to improve the spatial separation of the photogenerated charge carriers. This enables the composite with the Zn/Cd molar ratio of 1 : 1 to achieve a remarkable hydrogen production rate of 20.33 mmol g h and an apparent quantum efficiency (AQY) of 84.5% at 365 nm. By harnessing the synergistic effects of heterojunction and oxygen vacancies, this work provides a novel and effective strategy for designing high-performance photocatalysts for photocatalytic hydrogen production.
Ruthenium nitrosyl complexes with bidentate heterocycles: synthesis and their transformations in solution.
Brovko AO, Yakovlev IA, Kuratieva NV … +2 more , Sheven DG, Kostin GA
Dalton Trans · 2026 Jun · PMID 42366923 · Publisher ↗
A series of novel complexes with the general formula [RuNO(NH)(L)(NO)], where L is a bidentate ligand (bpym, bpy, or phen), were synthesized and characterized. -(NO, NO) and -(NO, NO) isomers were identified in the solid...
A series of novel complexes with the general formula [RuNO(NH)(L)(NO)], where L is a bidentate ligand (bpym, bpy, or phen), were synthesized and characterized. -(NO, NO) and -(NO, NO) isomers were identified in the solid state (SCXRD) and in DMSO solution (H NMR and IR spectroscopy). Their photochemical activity in DMSO was quantified under 450 nm irradiation using a flow-through system, allowing simultaneous IR and UV-Vis spectral monitoring. Quantum yields for photoinduced release of NO were determined to be 4.0 ± 0.8% for [RuNO(NH)(bpym)(NO)](NO) (1), 7.3 ± 0.2% for [RuNO(NH)(bpy)(NO)](NO)(PF) (2) and 3.1 ± 0.1% for [RuNO(NH)(phen)(NO)](NO) (3).
Distorted octahedral supramolecular cages based on spirobiindane with enhanced emission.
Xiao Y, Wang Z, Wang N … +7 more , Fu F, Zhong W, Li Z, Jiang Z, Wang J, Wang P, Chen M
Dalton Trans · 2026 Jun · PMID 42366909 · Publisher ↗
Although the structural framework for constructing regular polyhedral supramolecular cages from symmetric ligands is relatively well established, assembling distorted polyhedra using ligands of lower symmetry remains a c...
Although the structural framework for constructing regular polyhedral supramolecular cages from symmetric ligands is relatively well established, assembling distorted polyhedra using ligands of lower symmetry remains a considerable challenge. Herein, we report two distorted octahedral supramolecular cages, S1 and S2, based on a spirobiindane-derived rigid core with varying π-conjugation lengths and heteroatoms. The nearly perpendicular spirobiindane unit provides a rigid structural platform and promotes the formation of distorted cage-like structures. Octahedron S1 exhibited a high fluorescence quantum yield () of up to 72.87% in pure DMF, and the increased to 96.24% in a DMF/HO mixed solvent with 20% water content, surpassing that of most reported metal-organic cages. In contrast, the π-extended and heteroatom system S2 shows progressively red-shifted and aggregation-induced emission enhancement; however, the strong electron-withdrawing effect of the phenazine unit and the enlarged cavity size likely result in a significantly lower for S2 compared to S1. By reporting the synthesis of luminescent supramolecular cages with novel structures, this work further reveals how π-conjugation extension and heteroatoms modulate the emission behavior of supramolecular assemblies, thereby offering a new perspective for the rational design and construction of tunable luminescent supramolecular systems.
Luminescent new zirconium-based coordination polymer for selective and sensitive detection of dichromate ions in aqueous media.
Gaber M, Zaghloul B, Gado K … +2 more , Baraka A, Abuzalat O
Dalton Trans · 2026 Jun · PMID 42366861 · Publisher ↗
A new zirconium-based coordination polymer was synthesized through the coordination of zirconium(IV) ions with a newly synthesized π-conjugated amide-functionalized organic linker, namely ,'-(1,2-phenylene)dioxamic acid....
A new zirconium-based coordination polymer was synthesized through the coordination of zirconium(IV) ions with a newly synthesized π-conjugated amide-functionalized organic linker, namely ,'-(1,2-phenylene)dioxamic acid. The ligand was prepared by reacting oxalic acid dihydrate (2 mmol) with -phenylenediamine (1 mmol) in aqueous solution at 70 °C, forming a linker containing amide and carboxylate functionalities. The resulting linker solution was subsequently reacted with ZrOCl·8HO under hydrothermal conditions at 80 °C to form a robust and luminescent framework. The resulting compound 1 exhibits intense cyan photoluminescence under UV excitation at 365 nm and functions as a highly efficient optical sensor for hexavalent chromium (Cr(VI)) toxic ions in aqueous media. Upon exposure to CrO, the fluorescence is significantly quenched due to a synergistic mechanism involving photoinduced electron transfer (PET) and inner filter effect (IFE). A Stern-Volmer quenching constant () of 3.368 was obtained with a strong linear correlation ( = 0.9525) up to 2.1 ppm. The calculated limit of detection (LOD) is 13 ppb, allowing for trace-level sensing well below regulatory limits. X-ray photoelectron spectroscopy confirmed the redox transformation of Cr(VI) to Cr(III), validating not only sensing but also treatment through reduction to less toxic Cr(III). The compound 1 sensor also exhibits high selectivity over interfering ions, demonstrating its practical potential for real-time environmental monitoring of toxic Cr(VI) species.
Synergistic enhancement of photocatalytic sulfide oxidation in porphyrin-based binary systems.
Zhong HK, Feng JR, Huang ZH … +7 more , Wang GS, Wen TT, Huo YX, Zheng SY, Liu XH, Xue C, Zhou XT
Dalton Trans · 2026 Jun · PMID 42360771 · Publisher ↗
In this work, the synergistic effects in the photocatalytic oxidation of methyl phenyl sulfide (MPS) by metal-free/metalloporphyrins as photocatalysts and [Ru(bpy)] (RuBPY) as a photosensitizer were systematically invest...
In this work, the synergistic effects in the photocatalytic oxidation of methyl phenyl sulfide (MPS) by metal-free/metalloporphyrins as photocatalysts and [Ru(bpy)] (RuBPY) as a photosensitizer were systematically investigated. Metal-free porphyrins are capable of oxidizing MPS a singlet oxygen (O) pathway, despite their excited-state reduction potentials being lower than the oxidation potential of MPS. In contrast, metalloporphyrins containing Fe, Co, Cu, Mn, or Ni suppress O generation but exhibit higher excited-state reduction potentials than the oxidation potential of MPS. In binary systems (RuBPY : porphyrin = 25 : 5 μM), these metalloporphyrins promote MPS oxidation more effectively than their metal-free counterparts. Mechanistic studies reveal that upon excitation, electrons are transferred from the excited oxidation potential of metalloporphyrins to the excited reduction potential of RuBPY. This enables the excited reduction potential of metalloporphyrins to oxidize MPS to MPS˙, while the excited oxidation potential of RuBPY reduces O to superoxide (O˙). Thus, the porphyrin-based binary systems enhance photocatalytic MPS oxidation through two distinct pathways: with metal-free porphyrins by facilitating O˙ generation, and more notably, with metalloporphyrins, by promoting both O˙ and MPS˙ formation. This study provides insights into the rational design of homogeneous dual-component systems for photocatalytic organic oxidation, particularly those based on porphyrin-derived molecular photocatalysts.
Experimental and computational investigation of the intrinsic reactions of [UF]: formation of [UF(OCR)] & [U(OCR)] by reactions with carboxylic acids.
Lenze SJ, Handel MR, Hartman JA … +4 more , Zeiss AP, Ihabi A, Corcovilos TA, van Stipdonk MJ
Dalton Trans · 2026 Jun · PMID 42359830 · Publisher ↗
A major barrier to understanding the intrinsic reactivity of U(III) and U(IV) species is the limited experimental data available, largely because generating well-defined ions in these oxidation states for gas-phase studi...
A major barrier to understanding the intrinsic reactivity of U(III) and U(IV) species is the limited experimental data available, largely because generating well-defined ions in these oxidation states for gas-phase studies is challenging. Using tandem mass spectrometry, we can address this problem by preparing and isolating mid-valent uranium ions in a linear ion trap and examining their intrinsic chemistry through ion-molecule reactions. In this study, we focused on U(III) using the reagent ion [UF], which was generated by collisional activation of the precursor [UO(OC CHF)(HO)] within a linear ion trap mass spectrometer modified for ion-molecule reactivity. Building on our recent characterization of U(IV) carboxylate ions, [UF(OCR)] ( = 0-2; = 1-3), and the density-functional-theory energetics governing their formation, we now report two analogous U(III) derivatives, [UF(OCR)] and [U(OCR)], generated using formic, acetic, propionic, and acrylic acids. DFT calculations indicate that formation of U(III) carboxylates occurs by a metathesis mechanism, analogous to the previously reported U(IV) congeners, though slightly higher in energy. These newly accessible ions expand the range of uranium(III) species available for studies of intrinsic 5f-element reactivity.
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