Dalton Trans [JOURNAL]
Sun
200 papers
Metal dilution enabled quantum coherence in a planar Ni(III) dmit complex.
Tominaga R, Saha S, Miyake K … +5 more , Zenno H, Asada M, Nakamura T, Sekine Y, Hayami S
Dalton Trans · 2026 Jul · PMID 42318786 · Publisher ↗
Magnetically diluted (TBA)[NiAu(dmit)] samples were prepared by incorporating Ni(III) centres into an isostructural diamagnetic Au(dmit) lattice to reduce intermolecular antiferromagnetic interactions. The diluted comple...
Magnetically diluted (TBA)[NiAu(dmit)] samples were prepared by incorporating Ni(III) centres into an isostructural diamagnetic Au(dmit) lattice to reduce intermolecular antiferromagnetic interactions. The diluted complex exhibits slow relaxation, long spin-lattice relaxation and coherence times at 4 K, and clear Rabi oscillations, indicating that planar Ni(III)-dmit complexes can support molecular-spin-qubit behaviour.
Multivariate sulfur-functionalized MOFs shaped into alginate spheres for robust and reusable multidye water remediation.
García J, Escamilla P, Ferrando-Soria J … +3 more , Grancha T, Armentano D, Pardo E
Dalton Trans · 2026 Jun · PMID 42318772 · Full text
The removal of synthetic organic dyes from contaminated water remains a major environmental challenge, particularly under multicomponent and real-water conditions. Herein, we report a scalable adsorption platform based o...
The removal of synthetic organic dyes from contaminated water remains a major environmental challenge, particularly under multicomponent and real-water conditions. Herein, we report a scalable adsorption platform based on sulfur-functionalized metal-organic frameworks (MOFs) for efficient multidye removal. Three isoreticular MOFs, including a multivariate analogue incorporating methylcysteine and methionine functionalities, were evaluated using real water (Turia River, Spain). The multivariate MOF shows faster adsorption kinetics and achieves quantitative dye removal, outperforming its monofunctional counterparts. For practical implementation, the MOFs were immobilized into calcium alginate spherical beads (≈50 wt% loading), yielding mechanically robust composites that preserve crystallinity and porosity. The shaped materials retain high adsorption efficiency and can be reused over multiple cycles without performance loss. Under continuous-flow solid-phase extraction conditions, the system achieves >99% removal for all dyes, enabling rapid and effective water decontamination.
Boron-targeted H-atom transfer drives disproportionation of 2,1-benzazaborolyl radical anions beyond reversible Gomberg-Krause dimerization.
Hejda M, Dostál L, Mrózek O … +5 more , Růžička A, Lyčka A, Mikysek T, Jirásko R, Samsonov MA
Dalton Trans · 2026 Jun · PMID 42313520 · Publisher ↗
This contribution provides a detailed mechanistic insight into a remarkably complex reaction of neutral 1-Ph-2--butyl-1-1,2-benzazaborole (1) with elemental potassium in THF, yielding the known 10π-aromatic 1-2,1-benzaza...
This contribution provides a detailed mechanistic insight into a remarkably complex reaction of neutral 1-Ph-2--butyl-1-1,2-benzazaborole (1) with elemental potassium in THF, yielding the known 10π-aromatic 1-2,1-benzazaborolyl (2,1-) potassium salt (2), an isoelectronic species with indenyl potassium, along with a racemic mixture of a new potassium hydridoborate complex (3), formed together with 2 in 1 : 1 molar ratio. Unlike derivatives of isoelectronic 1-indene, which undergo various self-protonation processes under analogous conditions, for 1, we propose a completely different and rather complex, non-linear tandem mechanism. Key species are four enantiomeric pairs of short-lived, dimeric, diamagnetic intermediates, denoted α, β, ω1 and ω2, possessing structures related to Gomberg's dimer and Krause's adduct. Based on an exhaustive multinuclear NMR analysis of the reaction mixture, including experiments with -methylene deuterium-labelled starting compound 1-dn ( ∈ {0-2}) and the observation of a primary AKIE (/ ≫ 1), as well as a detailed analysis of full scan mass spectra and observed ions in ultrahigh-resolution LDI-MS data of the resulting mixture of isotopologues of the final product 3-dn ( ∈ {0-4}), comprising multiple isotopomers, in combination with probabilistic calculations, electrochemical studies, and DFT calculations, we were able to reconstruct the full sequence of reaction steps and pathways. The presented results support the involvement of various H-atom transfer (HAT) processes within pairs of radical-anionic species K+1˙-, proceeding through different transition states, and, most notably, reveal an extremely rare boron-targeted HAT. These findings provide a basis for developing synthetic routes to unconventional boron hydrides.
Recent advances in the development of optical chemosensors and chemodosimeters for the recognition of Hg.
Ghosh S, Roy S, Mahato S … +1 more , Roy P
Dalton Trans · 2026 Jun · PMID 42312928 · Publisher ↗
Mercury is one of the most harmful elements. It is commonly present as Hg ions. Its presence in the human body causes several health issues. Its detection by colorimetric and fluorogenic methods has been achieved by seve...
Mercury is one of the most harmful elements. It is commonly present as Hg ions. Its presence in the human body causes several health issues. Its detection by colorimetric and fluorogenic methods has been achieved by several research groups by the use of chemosensors and chemodosimeters. These chemosensors were constructed from several fluorophores, such as rhodamine, coumarin, tetraphenylethene, and quinoline. The presence of thio functionalities in them provides another opportunity for the recognition of the metal ion. This is possible using either chemosensors with a reversible binding nature or chemodosimeters where structural changes occur with breaking and forming several covalent bonds irreversibly. The presence and interaction of Hg with the probes cause significant alterations in their photophysical properties, enabling their application as sensors for the cation. About 135 recently published research articles are included for discussion. This discussion provides the recent progress in the development of chemosensors and chemodosimeters for the detection of Hg. At the end, future prospects in this research field are discussed.
Optical properties of a dual-use phosphor SrLaWO:Mn for optical thermometry and plant growth lighting.
Wang F, Chen H
Dalton Trans · 2026 Jun · PMID 42307480 · Publisher ↗
The development of Mn-activated luminescent materials with high optical thermometric sensitivity remains challenging. In this study, a series of novel red-emitting phosphors SrLaWO:Mn (0.002 ≤ ≤ 0.012) were successfully...
The development of Mn-activated luminescent materials with high optical thermometric sensitivity remains challenging. In this study, a series of novel red-emitting phosphors SrLaWO:Mn (0.002 ≤ ≤ 0.012) were successfully prepared by high-temperature solid-state reaction. A systematic investigation was conducted on the crystal structure, elemental composition, photoluminescence characteristics, temperature-dependent luminescence, fluorescence lifetime, and concentration quenching mechanism of this phosphor series. The emission spectrum of phosphor SrLaWO:Mn exhibits a broad band centered at 717 nm, attributed to the E → A and T → A transition of Mn, which corresponds to far-red emission. This spectral feature aligns well with the far-red absorption band of phytochrome P, making it highly suitable for plant photomorphogenesis applications. Moreover, phosphor SrLaWO:0.008Mn demonstrates exceptional optical thermometric performance, achieving a relative sensitivity () of 2.01% K. Given its outstanding luminescent and thermal sensing properties, phosphor SrLaWO:Mn emerges as a promising bifunctional material for applications in non-contact optical thermometry and energy-efficient plant growth lighting systems.
[FeFe]-hydrogenase biomimics incorporating redox-active ligands: tuning the oxidation chemistry of ferrocene-dichalcogenolate-bridged centres phosphine substitution.
Orton GRF, Cockcroft JK, Ringenberg MR … +2 more , Hartl F, Hogarth G
Dalton Trans · 2026 Jul · PMID 42306837 · Publisher ↗
Ferrocene-dichalcogenolate-bridged complexes, [Fe(CO){μ-E(η-CH)Fe(η-CH)E}] (E = S, Se), are [FeFe]-hydrogenase biomimics, in which the two redox-active centres lie in close proximity. Here we report the syntheses and ele...
Ferrocene-dichalcogenolate-bridged complexes, [Fe(CO){μ-E(η-CH)Fe(η-CH)E}] (E = S, Se), are [FeFe]-hydrogenase biomimics, in which the two redox-active centres lie in close proximity. Here we report the syntheses and electrochemical studies of phosphine-substituted derivatives, which allows tuning of the oxidation chemistry of the Fe centre, while (effectively) leaving that of the ferrocene centre unchanged. Mono-substituted [Fe(CO){μ-Se(η-CH)Fe(η-CH)Se}(PhP--tolyl)], chelated [Fe(CO){μ-E(η-CH)Fe(η-CH)E}(κ-dppv)] and bridged [Fe(CO){μ-E(η-CH)Fe(η-CH)E}(μ-dppf)] complexes have been prepared under carefully controlled reaction conditions, the selenium derivative giving higher yields. Crystal structures of [Fe(CO){μ-Se(η-CH)Fe(η-CH)Se}(κ-dppv)] and [Fe(CO){μ-Se(η-CH)Fe(η-CH)Se}(μ-dppf)] have been determined, which contain three closely located iron redox centres. Cyclic voltammetry (CV) and IR spectroelectrochemistry (IR SEC) have been used to understand changes occurring upon oxidation. Upon successive replacement of carbonyl(s), the oxidation potential of the Fe centre is lowered and in the dppv and dppf complexes it occurs prior to oxidation of the remote Fe(II) centre in the ferrocene-dithiolate bridge, as confirmed by IR SEC experiments. Dppf complexes contain three different iron oxidation centres, and three separate oxidation waves are identified in the CV of [Fe(CO){μ-Se(η-CH)Fe(η-CH)Se}(μ-dppf)]. DFT calculations have been used to better understand the likely structures of the oxidised species. They suggest that oxidation of the Fe centre results in a structural rearrangement to give a semi-bridging carbonyl, but no such species are observed by IR SEC, possibly due to the high rearrangement energies. IR SEC studies also suggest that for the dppf complexes, oxidation may be delocalised over several sites.
Photothermal amplification of Cu-porphyrin redox chemistry on TiC MXene for NIR-activated reactive oxygen species generation for the treatment of hepatocellular carcinoma.
Dey U, Ghosh A, Das N … +2 more , Singh A, Sahu SK
Dalton Trans · 2026 Jun · PMID 42306814 · Publisher ↗
Controlled generation and regulation of reactive oxygen species (ROS) remains challenging when photochemical and redox processes are combined for cancer-related applications. Photothermal regulation of metal-centred redo...
Controlled generation and regulation of reactive oxygen species (ROS) remains challenging when photochemical and redox processes are combined for cancer-related applications. Photothermal regulation of metal-centred redox kinetics provides a route to amplified ROS (O, ˙OH, O˙, .) generation in hybrid inorganic systems. In such systems, transition metal-mediated ROS generation is intrinsically governed by local coordination environments, redox kinetics, and energy-transfer pathways. Herein, we report a stepwise-assembled TiC@UCNP@Cu-TCPP@LA system in which the redox chemistry of Cu(II)-tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) is kinetically regulated by plasmon-assisted photothermal activation of TiC MXene under near-infrared (808 nm) irradiation. TiC nanosheets were integrated with aminated NaYF:Yb/Er/Nd upconversion nanoparticles (UCNPs) through interfacial hydrogen bonding. UCNPs serve as NIR-to-visible photonic intermediates for activating spatially segregated Cu-TCPP moieties covalently attached to the UCNP surface. This architecture suppresses π-π aggregation-induced ROS quenching, preserves the excited-state dynamics of Cu-TCPP, and facilitates efficient Förster resonance energy transfer (FRET) from the UCNPs. Under 808 nm irradiation, the integrated TiC component exhibits pronounced plasmon-derived photothermal behaviour (photothermal conversion efficiency ≈57%), which kinetically accelerates singlet oxygen (O) generation from photoexcited Cu-TCPP. Simultaneously, photothermal heating promotes intracellular Cu/Cu redox cycling and accelerates glutathione depletion and Fenton-like hydroxyl radical (˙OH) production, collectively amplifying chemodynamic reactivity. TiC-mediated photothermal activation yields ∼4-fold higher O and ∼3-fold greater ˙OH generation than the UCNP@Cu-TCPP@LA system. Beyond photothermal activation, TiC serves as a conductive support that facilitates interfacial charge and energy transfer processes under NIR irradiation. Functionalisation with lactobionic acid (LA) improves aqueous dispersibility and enables receptor-mediated cellular uptake. studies confirm pH-responsive behaviour, efficient intracellular ROS generation, and significant cancer cell apoptosis (∼78%) under 808 nm excitation, highlighting the functional relevance of plasmon-assisted photothermal amplification of Cu-porphyrin redox chemistry on TiC.
Hydroxide anion attack governs O-O bond formation in water oxidation catalysed by a mononuclear manganese complex.
Huo Q, Jamshidi M, Liu Z … +3 more , Longhurst M, Stranger R, Ariafard A
Dalton Trans · 2026 Jul · PMID 42305088 · Publisher ↗
Electrocatalytic water oxidation by the mononuclear Mn(II) pyridinophane complex [{PyN(Bu)}Mn(HO)] has been experimentally observed to occur under strongly basic conditions (pH = 12.2). In this work, the mechanism of thi...
Electrocatalytic water oxidation by the mononuclear Mn(II) pyridinophane complex [{PyN(Bu)}Mn(HO)] has been experimentally observed to occur under strongly basic conditions (pH = 12.2). In this work, the mechanism of this reaction has been re-examined using density functional theory (DFT) calculations at the SMD/M06-L-D3/def2-TZVP and SMD/B3LYP*-D3/def2-TZVP//SMD/M06-L-D3/def2-TZVP levels of theory. Previous studies have proposed that the active species responsible for O-O bond formation is the bis-oxo Mn(V) complex [{PyN(Bu)}Mn(O)], and that this step proceeds either through an oxo-oxo coupling (OOC) mechanism or a water nucleophilic attack (WNA) mechanism. However, we found that O-O coupling through these two mechanisms requires activation barriers of approximately 26 kcal mol, which are too high to be accessible under the employed reaction conditions. Based on our calculations, this crucial step proceeds the free hydroxide nucleophilic attack (FHNA) mechanism, in which hydroxide attacks the bis-oxo Mn(V) complex, with a calculated activation free energy of approximately 19 kcal mol. Further analysis reveals that in the O-O bond-forming step, both the nucleophilicity of the attacking species and the energy of the Mn d acceptor orbital play key roles in lowering the activation barrier. Our calculations show that the energy of this Mn d acceptor orbital can be tuned through modifications to the ligand backbone of the Mn pyridinophane complex. These computational findings may offer useful insights for the rational design of more effective catalysts for water oxidation.
Novel Fe cluster topology from a new hexadentate chelate: magnetic analysis by experimental, DFT, and magnetostructural correlation methods.
Diodati A, Brantley CL, Peralta JE … +4 more , Figueroa A, Dobrzycki L, Abboud KA, Christou G
Dalton Trans · 2026 Jul · PMID 42304714 · Publisher ↗
The new potentially hexadentate chelate ,'-bis(2-pyridylmethyl)-,'-bis(2-hydroxyethyl)-ethylenediamine (bphnH) has been synthesized. It possesses a mixed diol/diamine/dipyridine nature and has proven the source of two ne...
The new potentially hexadentate chelate ,'-bis(2-pyridylmethyl)-,'-bis(2-hydroxyethyl)-ethylenediamine (bphnH) has been synthesized. It possesses a mixed diol/diamine/dipyridine nature and has proven the source of two new Fe/oxo complexes with unprecedented structures. [FeO(bphnH)(bphnH)][Ce(NO)] (1) and [FeO(bphn)(NO)](NO) (2) contain pentadentate and hexadentate chelates, respectively. A three-pronged approach comprising fits of experimental magnetic susceptibility data, DFT computations and use of a magnetostructural correlation has been applied to analyse the variable-temperature magnetic properties of 2, the reliability of obtained pairwise exchange interactions, the occurrence and avoidance of overparameterization problems, and the quantitative determination of a very weak long-range interaction in a molecule also containing very strong and medium strength interactions.
Organotin(IV) compounds with potent cytotoxicity, DNA damage, cell cycle arrest, and pro-apoptotic effects.
Sharma S, Ögmundsdóttir MH, Ögmundsdóttir HM … +2 more , Sigurdsson ST, Damodaran KK
Dalton Trans · 2026 Jul · PMID 42304697 · Publisher ↗
Platinum-based anticancer agents exert their activity through DNA cross-linking but are limited by systemic toxicity, poor selectivity, and the emergence of drug resistance, underscoring the need for alternative mechanis...
Platinum-based anticancer agents exert their activity through DNA cross-linking but are limited by systemic toxicity, poor selectivity, and the emergence of drug resistance, underscoring the need for alternative mechanisms of action. We have selected organotin(IV) center with intrinsic cytotoxic potential and combined it with multifunctional ligands containing functional moieties that could enhance the anticancer efficacy, and synthesised two organotin(IV) complexes, BuSnL and PhSnL (L = benzyl 2-(diphenylphosphoryl)hydrazine-1-carbodithioate), to explore a non-cross-linking DNA-damaging strategy. Cellular uptake studies revealed substantial intracellular accumulation of both complexes, with preferential nuclear localization. cytotoxicity assays demonstrated potent antiproliferative activity against breast cancer T-47D cells, with BuSnL exhibiting an IC value of 0.32 ± 0.04 μM, representing an ≈88-fold increase in potency relative to cisplatin. Mechanistic investigations indicated that these complexes induce pronounced DNA damage, G1-phase cell cycle arrest, and intracellular ATP depletion, ultimately leading to apoptotic cell death. The DNA interaction studies suggest the possibility of a distinct binding mode compared to cisplatin, and we propose that the complex is coordinating to phosphate groups rather than nucleobase cross-linking. These findings indicate that organotin(IV) complexes are promising anticancer candidates that may offer a different mechanism of action, potentially overcoming the limitations of cisplatin.
Modulating central metal ions in metal-organic cages for enhanced CO photoreduction.
Tian Y, Chen L, Jiang J … +5 more , Lu Q, Yan Z, Shan G, Qin C, Zhao L
Dalton Trans · 2026 Jul · PMID 42301703 · Publisher ↗
Metal-organic cages are a class of excellent photocatalysts. In this work, TNC@Co and TNC@Fe were used as model systems to investigate the influence of metal nodes on the photocatalytic reduction of CO. The catalytic act...
Metal-organic cages are a class of excellent photocatalysts. In this work, TNC@Co and TNC@Fe were used as model systems to investigate the influence of metal nodes on the photocatalytic reduction of CO. The catalytic activity of TNC@Co reaches 18.8 mmol g h, which is 3.2 times higher than that of TNC@Fe. FTIR spectroscopy revealed that, compared to TNC@Fe, TNC@Co generates and accumulates reaction intermediates more rapidly, thereby significantly enhancing photocatalytic performance. This study provides experimental evidence for the design of highly efficient photocatalytic systems and offers crucial support for advancing CO catalytic conversion technologies.
Rational design of BODIPY-functionalized MOF photocatalysts for highly efficient hydrogen production.
Coşkun Z, Yıldız Gül E, Topaloğlu Aksoy B … +3 more , Seifi A, Tanrıverdi Eçik E, Çoşut B
Dalton Trans · 2026 Jul · PMID 42301270 · Publisher ↗
Photocatalytic hydrogen production through water reduction, driven by hydrogen's high energy density and environmental sustainability, represents a significant pathway for meeting future energy needs and is considered on...
Photocatalytic hydrogen production through water reduction, driven by hydrogen's high energy density and environmental sustainability, represents a significant pathway for meeting future energy needs and is considered one of the most promising strategies. A major challenge is developing a photocatalyst that is sustainable, stable, and environmentally friendly and has a large surface area. Although various MOF-based photocatalysts incorporating porphyrins, phthalocyanines, or other organic dyes have been extensively explored, studies utilizing BODIPY as a functional chromophore remain scarce. The combination of MOFs with BODIPY units offers a unique platform that couples the structural tunability and stability of MOFs with the excellent light-harvesting and electron-accepting properties of the BODIPY dyes. However, strategies for the systematic design and synthesis of BODIPY-MOF hybrid photocatalysts for hydrogen evolution are still very limited. In this study, the UiO-66-NH structure was modified with BODIPY compounds containing thiophene (BD2) and phenyl (BD4) units, resulting in the synthesis of BD2/UiO-66-NH and BD4/UiO-66-NH, respectively. As a result of the 6-hour photocatalytic water splitting experiments, the reaction kinetics of UiO-66-NH, BD2/UiO-66-NH, and BD4/UiO-66-NH were calculated to be 3013 μmol g h, 14 237 μmol g h (4.7-fold increase compared to UiO-66-NH), and 21 179 μmol g h (7-fold increase compared to UiO-66-NH), respectively. Based on the band structure and photoelectrochemical results, the observed behavior is consistent with the S-scheme charge-transfer pathway for the photocatalytic process. This study provides new insights into integrating BODIPY chromophores into MOF frameworks, establishing a promising design concept for the development of efficient dye-MOF hybrid photocatalysts for solar-to-hydrogen conversion.
Pyrene-based metal-organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) for photocatalytic applications.
Mo Q, Liu J
Dalton Trans · 2026 Jun · PMID 42300968 · Publisher ↗
Pyrene-based metal-organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have emerged as a distinctive class of photoactive crystalline materials for photocatalytic applications. The exceptional photoph...
Pyrene-based metal-organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have emerged as a distinctive class of photoactive crystalline materials for photocatalytic applications. The exceptional photophysical properties of pyrene, including strong visible-light absorption, long-lived excited states, high carrier mobility, and a strong tendency for π-π stacking, enable the construction of porous frameworks with tunable photoactive functions. This review provides a systematic overview of recent advances in the design, synthesis, and photocatalytic applications of pyrene-based MOFs and HOFs. Fundamental concepts such as light harvesting, exciton migration, charge separation, and energy transfer are discussed alongside key design strategies, including linker engineering, metal node selection, and supramolecular assembly. The fabrication of pyrene-based frameworks and their composites is summarized, highlighting methods such as stacking engineering, host-guest encapsulation, and self-assembly. Their applications in hydrogen evolution, CO reduction, HO generation, organic pollutant degradation, and organic transformations are critically evaluated, with an emphasis on structure-property relationships and mechanistic insights. Finally, current challenges, including limited charge separation, structural instability, and insufficient catalytic efficiency, are discussed, and future directions such as heterostructure engineering, thin-film processing, nanoscale and interfacial design, defect and donor-acceptor modulation, and combined -theoretical characterization are proposed. This review aims to provide a comprehensive design idea for the rational design and application of pyrene-based photoactive frameworks in sustainable photocatalysis.
Synergizing Ag alloying and urchin-like structure to steer formic acid oxidation toward the direct pathway on Pt nanocrystals in acidic medium.
Han Y, Sun H, Zhang Y … +3 more , Ma Y, Gong L, Zheng Y
Dalton Trans · 2026 Jul · PMID 42300959 · Publisher ↗
Developing efficient and CO-tolerant electrocatalysts for formic acid oxidation remains a critical challenge due to the sluggish kinetics and severe CO poisoning of Pt-based catalysts. Herein, we report a facile synthesi...
Developing efficient and CO-tolerant electrocatalysts for formic acid oxidation remains a critical challenge due to the sluggish kinetics and severe CO poisoning of Pt-based catalysts. Herein, we report a facile synthesis of urchin-like PtAg nanocrystals (PtAg NUs) with a densely branched architecture, which synergizes Ag alloying and unique morphological features to steer the reaction toward the direct pathway. When assessed for formic acid oxidation in acidic medium, PtAg NUs exhibit significantly enhanced performance compared to commercial Pt/C. Specifically, PtAg NUs show a lower onset potential (320 430 mV), a 17.6-fold higher direct pathway specific activity (0.88 0.05 mA cm), and a 3.9-fold higher indirect pathway specific activity (0.66 0.17 mA cm). Most notably, PtAg NUs demonstrate enhanced long-term stability, retaining nearly six times higher current after 3600 s (0.035 0.006 mA cm). Raman spectroscopy confirms that both direct and indirect pathways coexist, with Ag alloying steering the reaction toward a more direct pathway-dominant process. Density functional theory reveals that Ag alloying downshifts the d-band center, weakening CO adsorption and facilitating the COOH*-mediated pathway. The enhanced performance is attributed to the synergistic interplay of Ag electronic modification and the urchin-like geometric effects. This work highlights how synergizing Ag alloying and morphological engineering can steer formic acid oxidation toward the direct pathway, offering a rational design strategy for advanced Pt-based electrocatalysts.
Molecular engineering of a 2,5-dithiophen-2-yl-pyrrole-bridged terpyridine-Fe(II) coordination polymer toward multi-state electrochromic energy storage.
Song Y, Qiao H, Cheng L … +4 more , Wei Z, Lu B, Huang B, Tao J
Dalton Trans · 2026 Jul · PMID 42300954 · Publisher ↗
Electrochromic energy-storage materials are of great interest due to their ability to simultaneously achieve reversible color modulation and charge storage, with molecular engineering playing a key role in performance op...
Electrochromic energy-storage materials are of great interest due to their ability to simultaneously achieve reversible color modulation and charge storage, with molecular engineering playing a key role in performance optimization. Herein, a terpyridine-Fe-coordinated conjugated polymer (FeSNSTPy) incorporating a 2,5-dithiophen-2-yl-pyrrole (SNS) π-bridge was successfully constructed. The polymer exhibits a dual electrochromic response arising from SNS backbone doping and Fe(II)/Fe(III)-associated MLCT modulation. FeSNSTPy delivers an optical contrast of 34%, fast switching kinetics (/ = 2.4/2.5 s), and a high coloration efficiency of 626.54 cm C, together with good cycling stability (91% retention after 100 cycles and 77% after 250 cycles). Moreover, the FeSNSTPy film exhibits an areal capacitance of 2.74 mF cm at 0.1 mA cm, demonstrating its promising electrochemical energy-storage capability. This work provides a feasible strategy for developing multi-state electrochromic coordination polymers toward advanced electrochromic energy-storage applications.
NIR-II photothermal-thermoelectric effect-enhanced electrochemical sensing for dopamine detection in sweat.
Qiu W, Zhao L, Xiong H … +6 more , Qi H, Pan J, Wu H, Xu S, Ma Y, Shi X
Dalton Trans · 2026 Jul · PMID 42300950 · Publisher ↗
The accurate and non-invasive detection of dopamine (DA) in sweat is crucial for the early diagnosis of neurological diseases, but the selective and sensitive detection of DA in complex biological matrices still remains...
The accurate and non-invasive detection of dopamine (DA) in sweat is crucial for the early diagnosis of neurological diseases, but the selective and sensitive detection of DA in complex biological matrices still remains a challenge. This study presents a novel screen-printed electrode based on a ternary nanocomposite of gold nanobipyramid@copper selenide@MXene nanosheets (Au NBP@CuSe@MXene) for the highly sensitive and selective detection of DA. For the first time, Au NBPs with localized surface plasmon resonance (LSPR) in the near-infrared second window (NIR-II) are employed to enable a one-step, pretreatment-free detection strategy by leveraging the negligible background absorption of biological matrices. Under NIR-II irradiation, the Au NBP core generates an LSPR-induced photothermal effect, which can be harnessed by the CuSe shell to generate a thermoelectric field that significantly accelerates the interfacial electrocatalytic oxidation of DA. Besides, Au NBPs can generate LSPR hot carriers, which are injected into CuSe to participate in the redox process. Furthermore, the MXene substrate ensures efficient charge transport and structural stability. As a result, this ternary nanocomposite-based sensor exhibits a wide linear detection range for DA from 0.1 to 1000 μM. It achieves a detection limit of 0.107 μM under standard conditions, which is further reduced to 0.068 μM under NIR-II laser irradiation, demonstrating the effective signal amplification photothermal-thermoelectric coupling. This work provides a robust and innovative material platform that integrates photothermal, thermoelectric, and electrochemical mechanisms, paving the way for the development of next-generation, high-performance wearable sensors for non-invasive health monitoring.
Alkali-site lithium doping enables a high-performance NaFe(PO)(PO) cathode for sodium-ion batteries.
Sun Z, Cao W, Hu X … +1 more , Yang Z
Dalton Trans · 2026 Jul · PMID 42300944 · Publisher ↗
Iron-based polyanionic NaFe(PO)(PO) (N3F2PP) has emerged as a compelling cathode candidate for sodium-ion batteries (SIBs) owing to its cost-effectiveness and structural stability. Nevertheless, its practical application...
Iron-based polyanionic NaFe(PO)(PO) (N3F2PP) has emerged as a compelling cathode candidate for sodium-ion batteries (SIBs) owing to its cost-effectiveness and structural stability. Nevertheless, its practical application is constrained by intrinsically sluggish Na diffusion kinetics and limited accessible capacity. Herein, a trace Li substitution strategy at alkali sites was proposed to address these limitations. Partial substitution of Na with smaller Li induces localized lattice contraction and optimizes the local structural environment, thereby promoting Na transport. Moreover, Li incorporation subtly modifies the local Fe-O coordination environment, alleviating the lattice strain associated with the Fe/Fe redox reaction. As a result, the optimized NaLiFe(PO)(PO)@C (NLF2PP@C-0.05) cathode delivered a remarkable discharge capacity of 113.2 mAh g at 0.1 C, along with outstanding rate capability (84.1 mAh g at 20 C) and cycling stability (97.5% capacity retention after 2000 cycles at 20 C). This work highlights alkali-site substitution as a novel design paradigm for polyanionic cathodes, offering an effective complement to conventional Fe-site engineering strategies.
Regulation of the bis(triarylamine) conformation by auxiliary ligands in coordination polymers for modulation of redox activity.
Jin SY, Meng YR, Ji F … +4 more , Cai ZY, Liang Y, Zhang G, Su J
Dalton Trans · 2026 Jun · PMID 42300937 · Publisher ↗
By introducing auxiliary ligands of different lengths, four bis(triarylamine)-based coordination polymers were constructed, and their crystal structures and redox activities were studied. Structural analysis revealed tha...
By introducing auxiliary ligands of different lengths, four bis(triarylamine)-based coordination polymers were constructed, and their crystal structures and redox activities were studied. Structural analysis revealed that a higher degree of planarity in bis(triarylamine) units leads to lower oxidation potentials, which may promote the development of electrochromic materials.
Decoupling high-temperature phase transition and charge-transfer emission in a crown ether-based crystal.
Liu J, Yang X, Han S … +2 more , Zhang W, Shi P
Dalton Trans · 2026 Jul · PMID 42300932 · Publisher ↗
Crown ether-ammonium inclusion compounds have attracted great interest in the fields of supramolecular chemistry, crystal engineering, and molecular switches due to their tunable host-guest dynamics and stimuli-responsiv...
Crown ether-ammonium inclusion compounds have attracted great interest in the fields of supramolecular chemistry, crystal engineering, and molecular switches due to their tunable host-guest dynamics and stimuli-responsive phase transitions. However, most reported systems exhibit phase transitions only below room temperature, limiting practical applications, and their luminescence properties remain largely unexplored. Herein, we report a host-guest inclusion compound, [(2-fluorophenethylaminium)(18-crown-6)][PF] (1) that undergoes a reversible phase transition at 404 K, approaching the highest values reported in crown ether-based systems. Single-crystal X-ray diffraction confirms that the ammonium cation is tightly anchored within the 18-crown-6 cavity through N-H⋯O hydrogen bonds. Remarkably, the regioisomeric 3-fluoro (2) and 4-fluoro (3) analogues show no detectable phase transition, yet all three isomers display intense blue emission under 365 nm UV irradiation. This contrast demonstrates that 2-fluorine substitution is essential for the high-temperature transition, while luminescence arises from supramolecular confinement and does not depend on the fluorine substitution position. Density functional theory calculations support an intermolecular charge-transfer mechanism: the HOMO is localized on the crown ether oxygen atoms, the LUMO on the aromatic ring of the cation, with a calculated HOMO-LUMO gap of 4.49 eV. Collectively, these results demonstrate decoupling of the two functions, where the phase transition is governed by fluorine regiochemistry and emission is controlled by confinement effects. This decoupling provides a design principle for independently tuning thermal and optical properties in multifunctional molecular crystals.
A dye-loaded FeL cage for efficient photocatalytic C(sp)-H activation.
Zhang J, Shi Y, Wu Y … +3 more , Yang F, Jing X, Duan C
Dalton Trans · 2026 Jul · PMID 42300902 · Publisher ↗
We report the rational construction of a novel cationic metal-organic cage C1 featuring a well-defined FeL tetrahedral structure. C1 possesses a large inner cavity and robust openings, which enable it to act as an ideal...
We report the rational construction of a novel cationic metal-organic cage C1 featuring a well-defined FeL tetrahedral structure. C1 possesses a large inner cavity and robust openings, which enable it to act as an ideal supramolecular host to encapsulate the anionic photosensitizer anthraquinone-2,6-disulfonic acid disodium salt (AQDS) host-guest interactions to form a photoactive host-guest complex. Benefiting from the spatial confinement effect of the cage cavity, AQDS and reaction substrates are colocalized in the confined microenvironment, converting the diffusion controlled intermolecular reaction into a highly efficient pseudo-intramolecular process. This supramolecular photocatalytic system achieves efficient oxidation of C(sp)-H bonds under mild conditions, without relying on the high temperature and pressure protocols required by traditional synthetic methods, providing a valuable confinement strategy for the design of high performance photocatalytic systems.
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