Dalton Trans [JOURNAL]
Sun
200 papers
Spin-lattice relaxation of copper and vanadyl porphyrins in extended molecular framework materials.
Suzuki Y, Sato K, Wakizaka M … +2 more , Sakamoto R, Yamashita M
Dalton Trans · 2026 Jun · PMID 42300557 · Publisher ↗
Spin-lattice relaxation times () of Cu(II) and VO(IV) porphyrins in extended framework materials (covalent, hydrogen-bonded, and metal-organic frameworks) are investigated as prototypical molecular spin qubits. All frame...
Spin-lattice relaxation times () of Cu(II) and VO(IV) porphyrins in extended framework materials (covalent, hydrogen-bonded, and metal-organic frameworks) are investigated as prototypical molecular spin qubits. All framework materials studied here exhibit longer values than the corresponding metal tetraphenylporphyrin (MTPP) crystals.
A ligand in the metal salt sea: extreme metal-to-ligand ratios and the thermodynamic driving force of the halogen bond.
Yardan A
Dalton Trans · 2026 Jun · PMID 42300543 · Publisher ↗
This study presents the rational design, synthesis, and comprehensive structural elucidation of a novel series of halogenated coordination complexes featuring Cu(II), Co(II), Cd(II), and Mn(II) centers. By deliberately e...
This study presents the rational design, synthesis, and comprehensive structural elucidation of a novel series of halogenated coordination complexes featuring Cu(II), Co(II), Cd(II), and Mn(II) centers. By deliberately employing an extreme 10 : 1 metal-to-ligand stoichiometry, a supersaturated "metal salt sea" was successfully navigated to kinetically trap unique microcrystalline solid-state phases. Overcoming the inherent challenges of single-crystal growth, the intricate 3D architectures of these rapid-precipitation products were determined utilizing Powder X-ray Diffraction (PXRD) methodologies. Crystallographic analyses reveal a striking structural diversity, notably featuring highly asymmetric binuclear cores. The immense steric encumbrance of the chelating counter-anions forces the metal centers into unusual coordination environments, including a severely distorted 6-coordinate intermediate trapped along the Bailar twist pathway (between and geometries), alongside a validated square-pyramidal distortion ( = 0.303). Crucially, Quantum Theory of Atoms in Molecules (QTAIM) and Non-Covalent Interaction (NCI) analyses unmasked a highly localized Br⋯O halogen bond acting as a potent thermodynamic anchor (∼6.25 kcal mol), overriding classical steric expectations to dictate the ultimate coordination topology. Alongside this, Frontier Molecular Orbital (FMO) and 3D spin density mapping uncovered profound intramolecular electronic communication, revealing distinct Ligand-to-Metal Charge Transfer (LMCT) pathways and robust superexchange mechanisms. Translating these molecular-level interactions to macroscopic properties, morphological investigations Transmission Electron Microscopy (TEM) revealed a spectacular, metal-dependent nanoscale evolution. The macroscopic morphologies ranged from ultra-thin (∼5 nm) 1D nanowires-strictly dictated by Jahn-Teller distortions-and uniform nanorods to polymorphic networks, sub-50 nm polymeric clusters, and massive aggregates featuring sponge-like interstitial cavities. Finally, Thermogravimetric Analysis (TGA) demonstrated the remarkable thermal stability (up to 400-500 °C) of these robust networks. The flawless synergy between empirical structural models, theoretical simulations, and physicochemical characterizations provides profound insights into the predictive engineering of hierarchical supramolecular materials extreme concentration gradients.
Geometric control of Fe(I) intermediates in CO photoreduction by tetrahedral tripodal phosphine complexes.
Bento MA, Bandeira NAG, Miras HN … +6 more , Realista S, Gleeson M, Devid EJ, Brandão P, Rocha J, Martinho PN
Dalton Trans · 2026 Jun · PMID 42300529 · Publisher ↗
The development of homogeneous CO photoreduction catalysts based on Earth-abundant metals remains limited due to an insufficient mechanistic understanding of multielectron activation pathways. Here we show that a pseudot...
The development of homogeneous CO photoreduction catalysts based on Earth-abundant metals remains limited due to an insufficient mechanistic understanding of multielectron activation pathways. Here we show that a pseudotetrahedral Fe(II) complex supported by a tripodal tetradentate phosphine ligand, [Fe()(Cl)](BPh), functions as an efficient and selective molecular catalyst for visible-light-driven CO-to-CO conversion. Under the optimized conditions in acetonitrile, [Fe()(Cl)](BPh) achieves turnover numbers exceeding 1300, turnover frequencies of up to 445 h, and quantum yields of up to 0.64%, placing it among the most active Fe-based molecular catalysts for CO photoreduction. Electrochemical, spectroelectrochemical, fluorescence quenching, and high-resolution ESI-MS measurements, supported by computational studies, reveal that catalysis proceeds a one-electron-reduced Fe(I) acetonitrile adduct formed by ligand substitution of the Fe(II) precursor. This Fe(I) species promotes CO binding and proton-coupled reduction through well-defined Fe(I/II) intermediates, culminating in CO release and regeneration of the active complex. The CO-release step is found to be the rate-determining step (Δ = 12.9 kcal mol) with the generation of a Fe(II) complex displaying a coordination vacancy. The addition of a new acetonitrile molecule in tandem with one electron reduction regenerates the catalytically active species. These results demonstrate that pseudotetrahedral PN coordination environments stabilize reactive Fe(I) intermediates essential for CO activation, offering mechanistic design principles towards next-generation iron catalysts.
High-entropy LDH coupled with Ru nanoclusters for efficient overall seawater splitting.
Li X, Tang R, Liu J … +5 more , Li Y, Liang L, Huang W, Hao Q, Liu H
Dalton Trans · 2026 Jun · PMID 42300523 · Publisher ↗
This study reports a bifunctional high-entropy MnFeCoNiCu LDH electrocatalyst decorated with Ru nanoclusters for durable seawater electrolysis. The heterostructure facilitates efficient charge transfer, delivering a low...
This study reports a bifunctional high-entropy MnFeCoNiCu LDH electrocatalyst decorated with Ru nanoclusters for durable seawater electrolysis. The heterostructure facilitates efficient charge transfer, delivering a low cell voltage of 1.70 V at 10 mA cm for overall seawater splitting. Remarkably, it sustains stable operation for 50 hours at an industrial current density of 300 mA cm. Theoretical insights suggest that the Ru nanoclusters optimize the electronic structure, establishing a promising route for large-scale green hydrogen production.
Doubly reduced phthalocyanine complexes of V(IV), Cu(II), and Sn(II): synthesis, structure, and spin dynamics.
Faraonov MA, Romanenko NR, Ivanov TE … +7 more , Shmakov AS, Akimov AV, Kuzmin AV, Khasanov SS, Otsuka A, Kitagawa H, Konarev DV
Dalton Trans · 2026 Jun · PMID 42300490 · Publisher ↗
Doubly reduced phthalocyanine complexes remain largely unexplored despite their potential relevance for molecular spin-based applications. Herein, we report the synthesis of a series of crystalline complexes, {cryptand(C...
Doubly reduced phthalocyanine complexes remain largely unexplored despite their potential relevance for molecular spin-based applications. Herein, we report the synthesis of a series of crystalline complexes, {cryptand(Cs)}[M(Pc)]·CH (M = VO, Cu, and Sn, = 1.0-1.3), obtained reduction of the corresponding metal phthalocyanines with cesium anthracenide in toluene. X-ray diffraction, optical spectroscopy, EPR spectroscopy, and magnetic measurements demonstrate ligand-centered two-electron reduction, affording spin-free (Pc) ligands while preserving the metal oxidation states. The vanadyl and copper complexes exhibit isolated = 1/2 spin systems, whereas the tin analogue is diamagnetic. Continuous-wave and pulsed EPR spectroscopy, supported by magnetic susceptibility data, reveal slow magnetic relaxation and quantum coherence in the paramagnetic complexes. In particular, the copper complex shows field-induced slow relaxation with relaxation times up to 0.1 s. Spin coherence was observed in magnetically diluted vanadyl and copper systems, including crystalline dispersions and frozen solutions. The key role of the sample preparation strategy in relaxation behavior was demonstrated. These findings demonstrate that doubly reduced phthalocyanine complexes can serve as robust platforms for molecular = 1/2 spin qubits. Additionally, the straightforward reductive synthetic approach provides access to phthalocyanine-based systems that are mostly poorly soluble, opening new opportunities for the design of functional molecular materials.
Iridium(I)-corrorin complexes as green-light photosensitizers for singlet oxygen.
Wang Y, Wu Y, Wang L … +5 more , Sang L, Cao J, Furuta H, Xue S, Feng R
Dalton Trans · 2026 Jun · PMID 42300452 · Publisher ↗
Two mononuclear Ir(I)-corrorin complexes, FPh-Ir and Py-Ir, featuring peripheral -N,N' dipyrrin coordination, were structurally characterized and shown to efficiently photosensitize singlet oxygen under green light ( = 0...
Two mononuclear Ir(I)-corrorin complexes, FPh-Ir and Py-Ir, featuring peripheral -N,N' dipyrrin coordination, were structurally characterized and shown to efficiently photosensitize singlet oxygen under green light ( = 0.65-0.69 in CHCN). TD-DFT supports a near-resonant S → T intersystem-crossing pathway with appreciable spin-orbit coupling.
Ultra-wideband absorption-polarization conversion function switchable terahertz metamaterial.
Zhao Y, Zhao C, Liu N … +1 more , Cui Z
Dalton Trans · 2026 Jun · PMID 42300426 · Publisher ↗
This paper presents a bifunctional reconfigurable terahertz metamaterial device that integrates ultra-wideband absorption and high-efficiency broadband polarization conversion functionalities based on the phase-change ma...
This paper presents a bifunctional reconfigurable terahertz metamaterial device that integrates ultra-wideband absorption and high-efficiency broadband polarization conversion functionalities based on the phase-change material vanadium dioxide (VO). By exploiting the reversible insulator-to-metal phase transition of VO near 68 °C, the device achieves dynamic switching between two distinct electromagnetic response mechanisms. When VO is in its insulating state, the device operates as a broadband linear cross-polarization converter. Upon transitioning to the metallic state, the device functions as an ultra-wideband perfect absorber. The physical mechanisms underlying the dual functionality are elucidated through surface current distribution analysis, electric field monitoring, impedance matching theory, and equivalent electromagnetic parameter extraction. Comprehensive parametric studies reveal the influence of key structural dimensions on device performance, while angular dependence analyses demonstrate excellent polarization insensitivity and wide-incidence-angle stability in both operational modes. Compared with recently reported terahertz devices, the proposed design exhibits superior bandwidth performance, compact structural dimensions, and dynamic functional reconfigurability, making it a promising candidate for applications in intelligent stealth systems, terahertz imaging, optical switching, and advanced communication technologies.
Rare-earth orthoferrites (RFeO, R = La, Y) as next-generation electrode materials for high-performance supercapacitors.
Iqbal A, Anwer AH, Benamor A … +4 more , Arshad M, Ahmad N, Khatoon T, Ahmad N
Dalton Trans · 2026 Jun · PMID 42300415 · Publisher ↗
This study addresses the synthesis and electrochemical assessment of nanocrystalline orthoferrites (RFeO, R = La and Y) synthesized a sol-gel auto-combustion method. The synthesized orthoferrites were systematically cha...
This study addresses the synthesis and electrochemical assessment of nanocrystalline orthoferrites (RFeO, R = La and Y) synthesized a sol-gel auto-combustion method. The synthesized orthoferrites were systematically characterized for their structural, morphological, and electrochemical properties. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that both samples crystallized in a single-phase orthorhombic perovskite structure, with nanoscale domains. Upon their assessment as supercapacitor electrode materials, LaFeO exhibited a remarkably high specific capacitance of 815.6 F g at 1.0 A g, which is nearly twice that of YFeO. Furthermore, LaFeO retained 88-90% of its initial capacitance after 10 000 galvanostatic charge-discharge cycles, demonstrating its exceptional cycling resilience. The superior electrochemical performance of LaFeO is attributed to its electronic structure and optimized morphology and surface area, which facilitate effective ion diffusion and reversible redox reactions of Fe/Fe at the electrode-electrolyte interface. These characteristics lead to enhanced charge storage kinetics and structural robustness during repeated cycling. This excellent electrochemical performance, combined with a cost-effective and scalable synthesis, demonstrated LaFeO to be a promising electrode material for next-generation high-performance supercapacitor applications.
Synthesis and characterisation of novel dipyridine and pyridinyl benzoquinoline complexes of zinc and nickel.
Killian L, Olarte Loyo A, de Ridder RRPAM … +2 more , Lutz M, Thevenon A
Dalton Trans · 2026 Jun · PMID 42300413 · Full text
Dipyridine and pyridinyl benzoquinoline ligands and their coordination chemistry with nickel and zinc are described. The pyridinyl benzoquinoline ligand was synthesised through the photochemical Mallory reaction of the d...
Dipyridine and pyridinyl benzoquinoline ligands and their coordination chemistry with nickel and zinc are described. The pyridinyl benzoquinoline ligand was synthesised through the photochemical Mallory reaction of the dipyridine ligand. The zinc complexes adopt distorted tetrahedral geometries, featuring one coordinated dipyridine or pyridinyl benzoquinoline ligand, with two chlorides completing the first coordination sphere. In contrast, the nickel complexes adopt octahedral geometries with two bidentate ligands and two coordinating chlorides per metal centre. Using cyclic voltammetry, the redox behaviour of all complexes was investigated, revealing both ligand- and metal-based reduction, as well as surprising catalytic reactivity with DCM. Together, this work explores the synthesis and coordination chemistry of two new ligands of the uncommon dipyridine family.
Understanding the reactivity and activation barrier origins in the cycloaddition of triplet pnictinidenes with phenylacetylene.
Zhang ZF, Su MD
Dalton Trans · 2026 Jun · PMID 42300407 · Publisher ↗
This study investigates the mechanistic details of the [1 + 2] cycloaddition of phenylacetylene (Ar'CCH;) with triplet monomeric pnictinidenes (; G15 = Group 15 elements). The calculated results consistently support the...
This study investigates the mechanistic details of the [1 + 2] cycloaddition of phenylacetylene (Ar'CCH;) with triplet monomeric pnictinidenes (; G15 = Group 15 elements). The calculated results consistently support the greater stability of the triplet state () over the corresponding singlet state (). Furthermore, a gradual increase in singlet-triplet splitting is observed down the Group 15 series, highlighting the enhanced preference for triplet ground states among the heavier pnictogens. The origin of this trend is attributable to the relativistic inert s-pair effect and the concomitant non-hybridization effect. Theoretical results indicate that the reaction proceeds the pathway: + Ar'CCH → → → → , while activation strain model analysis reveals that the activation barrier is primarily governed by the deformation energy of Ar'CCH. More specifically, the present findings demonstrate that the atomic radius of the Group 15 center critically influences the activation barrier of the [1 + 2] cycloaddition, such that increasing the size of the G15 element in leads to higher barriers for reaction with Ar'CCH. Overall, this study provides a qualitative rationalization of the reaction energetics and evaluates the feasibility of the proposed experimental observations.
Ligand flexibility and counterion-driven diversity in morpholine-based Cd(II), Cu(II), Zn(II), and Ni(II) complexes: crystallographic, computational, and cytotoxicity insights.
Ahmadi M, Rezaeivala M, Zeynaloo E … +3 more , Yang YP, Gable RW, Khetrapal N
Dalton Trans · 2026 Jun · PMID 42300386 · Publisher ↗
Counterion identity and ligand flexibility play crucial yet often overlooked roles in governing structural properties and influencing functional behavior of metal complexes. We report a systematic investigation of a seri...
Counterion identity and ligand flexibility play crucial yet often overlooked roles in governing structural properties and influencing functional behavior of metal complexes. We report a systematic investigation of a series of morpholine-based Cd(II), Cu(II), Zn(II), and Ni(II) complexes that demonstrate how subtle variations in counterion identity and the donor environment can profoundly influence solid-state architectures, supramolecular motifs, and anticancer activity. Single-crystal X-ray diffraction reveals an unusual Cd(II) mixed-crystal system, previously reported to contain both a neutral [CdL(NO)] species with a staggered -(NO) motif and an ionic [CdL(HO)(NO)]NO species cocrystallized in a single lattice. DFT calculations of the experimental structure reveal spatial separation of the HOMO (localized on the neutral 2a site) and LUMO (on the ionic 2b site), providing an electronic rationale for the solid-state stabilization of 2b despite its thermodynamic instability in solution. In contrast, the perchlorate analogues of Cd(II) and Cu(II) form discrete chair-like supramolecular dimers mediated by N-H⋯Cl hydrogen bonding. Expanding the scope, a series of Ni(II) complexes featuring stepwise substitution of monodentate ligands (HO, CHCN, BuNC) reveal geometric isomerism in the HO complex and the formation of Ni-C bonds in the BuNC derivative, with all three structures exhibiting consistent equatorial coordination by the monodentate donors. This O → N → C donor progression is supported by crystallographic, spectroscopic, and conductivity data. Cytotoxicity assays reveal differences in activity among the complexes, with trends consistent with an influence of counterion identity; however, these observations remain preliminary due to the absence of complementary control experiments and stability under physiological conditions.
Evaluating Ce → Tb → Eu cascade sensitization in LiSrY(BO) for near-UV excited white emission.
Chen X, Cong R, Yang T
Dalton Trans · 2026 Jun · PMID 42300384 · Publisher ↗
Phosphor-converted white light-emitting diodes (pc-WLEDs) based on near-ultraviolet (NUV) excitation require single-phase phosphors that can simultaneously balance efficient energy transfer and well-distributed multi-col...
Phosphor-converted white light-emitting diodes (pc-WLEDs) based on near-ultraviolet (NUV) excitation require single-phase phosphors that can simultaneously balance efficient energy transfer and well-distributed multi-colour emission. Although Ce/Tb/Eu co-doping has been widely explored across various host lattices as a general strategy for white-light generation, its success strongly depends on the host lattice, which must simultaneously satisfy suitable excitation matching, efficient energy transfer, and good thermal stability. In this work, the borate host LiSrY(BO) (LSYB), which crystallizes in the trigonal space group 3̄1, is investigated as a host lattice for evaluating cascade sensitization. Benefiting from the broad NUV absorption and small Stokes shift of Ce, together with the previously identified Tb → Eu energy transfer in this host, the feasibility of constructing a Ce → Tb → Eu cascade pathway is rationally evaluated. Photoluminescence spectra and lifetime analyses confirm efficient Ce → Tb and Tb → Eu energy transfer processes, enabling stepwise spectral evolution from blue to green and ultimately to white light upon Eu incorporation. An optimized composition, LiSr(YCeTbEu)(BO), exhibits near-white emission with CIE coordinates of (0.3030, 0.3351) under 335 nm excitation and a correlated color temperature of 6989 K. The phosphor retains 60.47% of its emission intensity at 423 K, indicating good thermal stability. This work demonstrates that LSYB is a suitable host for Ce-sensitized cascade energy transfer, providing insight into host-dependent design of single-phase white-emitting phosphors, particularly in balancing cascade energy transfer and luminescence efficiency.
Iridium(III) polypyridyl and cyclometalated complexes for DNA targeting, bioimaging, and light-activated therapeutics: recent progress, mechanistic insights, and emerging design strategies-a mini review.
Aderinto SO, Thomas JA
Dalton Trans · 2026 Jun · PMID 42300374 · Publisher ↗
Iridium(III) polypyridyl and cyclometalated complexes have emerged as highly versatile coordination compounds with applications spanning photocatalysis, optoelectronics, bioimaging, and photodynamic therapy. Whilst ruthe...
Iridium(III) polypyridyl and cyclometalated complexes have emerged as highly versatile coordination compounds with applications spanning photocatalysis, optoelectronics, bioimaging, and photodynamic therapy. Whilst ruthenium(II) polypyridyl complexes have historically dominated nucleic acid recognition studies, iridium(III) systems possess distinct physicochemical advantages arising from strong spin-orbit coupling, tuneable metal-to-ligand charge-transfer (MLCT) states, long-lived triplet emission, and exceptional photostability. Despite these favourable features, their development as DNA-targeting agents remains comparatively underexplored, and mechanistic understanding lags behind that of ruthenium(II) counterparts. This review provides a structured overview of the recent advances in Ir(III) polypyridyl and cyclometalated complexes for DNA binding, luminescent sensing, and light-activated cytotoxicity. Particular emphasis is placed on structure-activity relationships, excited-state processes governing DNA-responsive luminescence, and photocleavage mechanisms. Comparisons with ruthenium(II) systems are drawn throughout to highlight iridium-specific design logic. Finally, current challenges and future research directions are identified to guide the rational development of multifunctional iridium(III) complexes for medicinal inorganic chemistry and therapeutic applications.
Magnetization dynamics in a Dy based 2D coordination network bridged by a nitronyl nitroxide radical with a CN group.
Jin CY, Li H, Zhou Y … +3 more , Tang J, Cheng P, Li L
Dalton Trans · 2026 Jun · PMID 42300362 · Publisher ↗
A new family of Ln-radical coordination networks {[Ln(hfac)](NIT-PhCN)} (Ln(III) = Gd 1, Tb 2 and Dy 3; hfac = hexafluoroacetylacetonate) was constructed by the reaction of the NIT-PhCN nitronyl niroxide radical (NIT-PhC...
A new family of Ln-radical coordination networks {[Ln(hfac)](NIT-PhCN)} (Ln(III) = Gd 1, Tb 2 and Dy 3; hfac = hexafluoroacetylacetonate) was constructed by the reaction of the NIT-PhCN nitronyl niroxide radical (NIT-PhCN = 2-(4'-cyanophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) with Ln(hfac) salts. The crystallographic investigations exhibit that the NIT-PhCN radical acts as a tridenate linker to connect three Ln ions its NIT moiety and the CN group in a μ-η:η:η fashion, giving rise to a 2D coordination network incorporating [Ln(NIT)] nodes featuring the [Ln-NIT-Ln-NIT-Ln] motif. The magnetic study shows that the radicals are weakly ferromagnetically coupled with lanthanides, in which the magnetic exchange for the Gd derivative is determined as 1.52 cm. Remarkably, the Dy derivative shows slow relaxation of magnetization with an effective energy barrier to spin reversal of = 32.26 K.
Nickel complexes supported by a new class of fused imidazonaphthyridine tridentate N,N,N-ligands for ethylene oligomerization and isolation of a key Ni-Al intermediate.
Zuo J, Li H, Hu C … +2 more , Zhao MX, Zhang J
Dalton Trans · 2026 Jun · PMID 42300265 · Publisher ↗
A series of 9-imino-imidazo[1,2-][1,7]naphthyridine ligands and their nickel complexes were synthesized and structurally characterized by single-crystal X-ray crystallography. X-ray diffraction analysis revealed that 9-i...
A series of 9-imino-imidazo[1,2-][1,7]naphthyridine ligands and their nickel complexes were synthesized and structurally characterized by single-crystal X-ray crystallography. X-ray diffraction analysis revealed that 9-imino-imidazo[1,2-][1,7]naphthyridines were used as tridentate ligands in most cases. Nickel complex Ni2 has a five-coordinate distorted square pyramidal geometry, in which the nickel is coordinated with three nitrogen atoms of the 9-imino-imidazo[1,2-][1,7]naphthyridine ligand and two chlorines. Nickel complexes Ni1, Ni3 and Ni5 displayed a six-coordinate distorted octahedral geometry upon coordination with a solvent molecule. Upon activation with diethylaluminum chloride (EtAlCl), high catalytic activity up to 1.20 × 10 g mol(Ni) h and high selectivity for butenes (95.9%) and 1-butene (99.0%) could be achieved using Ni1 as a catalyst. A higher activity of up to 2.06 × 10 g mol(Ni) h was observed in the Ni1/EtAlCl system with the addition of 10 equiv. of PPh as an auxiliary ligand. Isolation and structural characterization of a key Ni-Al intermediate provided crystallographic evidence of the role of a co-catalyst in the activation of the Ni precatalyst.
Gradually changing the fraction of clusters and nanoparticles in Au/WO-derived photocatalysts for HO synthesis.
Adnan RH, Osborn DJ, Yan S … +5 more , Shichibu Y, Nakajima H, Konishi K, Metha GF, Andersson GG
Dalton Trans · 2026 Jun · PMID 42300250 · Publisher ↗
Atomically-precise ligand-protected gold (Au) clusters have emerged as a promising co-catalyst in a wide range of reactions. It is known that the Au cocatalyst size plays a defining role in photocatalytic performance. Ho...
Atomically-precise ligand-protected gold (Au) clusters have emerged as a promising co-catalyst in a wide range of reactions. It is known that the Au cocatalyst size plays a defining role in photocatalytic performance. However, Au size effects have not been fully established for the size transition from clusters (<2.2 nm) to nanoparticles (>2.2 nm) in photocatalytic hydrogen peroxide (HO) synthesis. Using the [Au(dppe)Cl]Cl cluster (Au for convenience) as a cocatalyst deposited onto WO, we investigated the effects of Au size and the fraction of clusters and nanoparticles on the photocatalytic activity in HO synthesis by gradually changing the calcination temperature. Increasing the calcination temperature gradually increases the Au size and the fraction of aggregated species (nanoparticles). Uncalcined Au/WO (all cluster species) is photocatalytically inactive. The Au/WO-derived photocatalysts only exhibit photoactivity in HO production after calcination with increasing activity as the Au size and the fraction of nanoparticles increase. The high activity of calcined Au/WO is attributed to the formation of a strong metal-support interaction that promotes charge separation and transfer, together with the formation of larger Au particles. Calcined Au/WO (all nanoparticles) at 200 °C exhibits the highest HO production yield (2.1 mM) and rate (21 mM g h) with an apparent quantum yield of 1.27% under violet (∼405 nm) light irradiation. This work unravels the effects of Au cocatalyst size, the fraction of clusters and nanoparticles, and calcination temperature on the activity of Au/WO-derived photocatalysts in HO synthesis.
Triphenylene chromophore enhances emission in Au/Cu heterometallic complexes.
Ahmad J, Atencio AP, Ward JS … +4 more , Engeser M, Rissanen K, Angurell I, Rodríguez L
Dalton Trans · 2026 Jun · PMID 42300246 · Publisher ↗
Heterometallic Au(I)-Cu(I) assemblies are attractive luminescent platforms due to synergistic metallophilic interactions and enhanced spin-orbit coupling. We report a new family of Au(I)-Cu(I) complexes incorporating a r...
Heterometallic Au(I)-Cu(I) assemblies are attractive luminescent platforms due to synergistic metallophilic interactions and enhanced spin-orbit coupling. We report a new family of Au(I)-Cu(I) complexes incorporating a rigid 2-ethynyltriphenylene chromophore and a pyridyldiphenylphosphine auxiliary ligand. Stoichiometric reactions between a mononuclear alkynyl gold(I) precursor and Cu(I) salts bearing different counterions (PF, OTf, BF) afford AuCu assemblies whose structures and packing are strongly counterion-dependent. Single-crystal X-ray diffraction reveals Au-Cu interactions supported by Cu-N(pyridyl) and Cu⋯π(alkynyl) contacts. The photophysical studies show counterion-modulated dual fluorescence/phosphorescence emission in solution, with phosphorescence enhanced under inert conditions. Upon immobilization in polymer matrices, all heterometallic complexes display efficient room-temperature phosphorescence with quantum yields of up to 40% and millisecond lifetimes. These results highlight the role of counterions and matrix rigidification in controlling excited-state deactivation in heterometallic coinage-metal systems.
A supramolecular CS adduct: dynamic and interaction energy considerations of an orbiting S motif from MD + EDA calculations.
Paco-Chipana M, Muñoz-Castro A
Dalton Trans · 2026 Jun · PMID 42300207 · Publisher ↗
Dynamics of supramolecular complexes serve to rationalize the constant motion inherent to the formation of non-covalent adducts. Here, the CS adduct is evaluated through the combined molecular dynamics energy decompositi...
Dynamics of supramolecular complexes serve to rationalize the constant motion inherent to the formation of non-covalent adducts. Here, the CS adduct is evaluated through the combined molecular dynamics energy decomposition analysis approach (MD + EDA), unraveling the constant orbit-like motion of S around the C fullerene globe, showing comparable supramolecular interaction energies for the entire dynamic process, arising from a balance between stabilizing (electrostatic, London dispersion, orbital) and destabilizing (Pauli repulsion) forces. Thus, molecular dynamics simulations reveal the dynamic flexibility, with the S ring freely reorienting in relation to the C surface, remaining at a similar distance with similar interaction energy. The charge transfer analysis indicates negligible net electron transfer, but interestingly, the calculated electronic coupling and charge hopping rates suggest efficient charge transport. These findings highlight the delicate interplay of weak non-covalent interactions governing the formation of the C-S system and its potential for supramolecular charge transport applications, combining dynamic adaptability with specific binding properties for applications in supramolecular chemistry and related fields.
[Ru(bpy)(dppz)] encapsulated isostructural In-MOFs: a comparative study of their photoluminescence and photoredox catalytic activities.
Kim J, Kim CG, Lee J … +1 more , Huh S
Dalton Trans · 2026 Jun · PMID 42300194 · Publisher ↗
The large cationic [Ru(bpy)(dppz)] complex was encapsulated within the channels of two isostructural In-MOFs with distinct pore environments, and the resulting Ru(bpy)(dppz)@In-MOFs were utilized as highly recyclable het...
The large cationic [Ru(bpy)(dppz)] complex was encapsulated within the channels of two isostructural In-MOFs with distinct pore environments, and the resulting Ru(bpy)(dppz)@In-MOFs were utilized as highly recyclable heterogeneous visible-light photoredox catalysts.
CoSe/CoSe Mott-Schottky heterostructures embedded in porous carbon nanofibers toward efficient bifunctional catalysis in zinc-air batteries.
Song Y, Zhang D, Zhang Y … +1 more , Deng C
Dalton Trans · 2026 Jun · PMID 42300191 · Publisher ↗
The exploration of highly efficient bifunctional oxygen electrocatalysts is crucial for zinc-air batteries (ZABs). Transition metal selenides with low cost and high catalytic activity have demonstrated considerable poten...
The exploration of highly efficient bifunctional oxygen electrocatalysts is crucial for zinc-air batteries (ZABs). Transition metal selenides with low cost and high catalytic activity have demonstrated considerable potential in the field of catalysis. Herein, a novel CoSe/CoSe Mott-Schottky heterostructure is embedded in a porous, N-doped carbon (PNC) nanofiber network to fabricate a CoSe/CoSe@PNC bifunctional catalyst for ZABs. Theoretical analyses reveal that the CoSe/CoSe heterointerface induces a strong built-in electric field, which effectively optimizes the adsorption of oxygen intermediates and promotes bifunctional catalytic behavior. Experimental results demonstrate that the PNC nanofiber network provides high electrical conductivity and effectively prevents the heterostructures from agglomerating during cycling. Benefitting from both advantages, the CoSe/CoSe@PNC catalyst achieves remarkable bifunctional activity and superior stability. Integrated with a CoSe/CoSe@PNC air cathode, an aqueous ZAB is assembled, and it exhibits a peak power density of 215.13 mW cm and high stability during long-term cycling (400 h). Furthermore, the solid-state ZAB with flexible CoSe/CoSe@PNC shows superior reliability and high stability under various mechanical deformations. Thus, this study provides an effective strategy for the design of nonprecious-metal-based oxygen electrocatalysts and promotes the development of high-performance ZABs for diverse working conditions.
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