Extensive efforts in supramolecular chemistry have focused on employing ligands with fluorescence properties. In this study, a new dipyridyl indolocarbazole scaffold () was synthesized and, for the first time, employed in coordination-driven self-assembly with diruthenium (Ru) linkers (, , , and ). Notably, selective formation of [1 + 1] or [2 + 2] assemblies was achieved depending on the type of di-Ru(II) linker: , , and yielded [1 + 1] assemblies, whereas Ruox (oxalate-linked di-Ru(II)) produced a [2 + 2] assembly. The geometric relationship between the dipyridyl indolocarbazole and di-Ru(II) units in the resulting assemblies was further investigated. The solid-state structures of the obtained supramolecules were confirmed using X-ray crystallography, revealing that long Ru linkers formed planar "□"-shape supramolecules, whereas short Ru linkers produced three-dimensional "["-shape supramolecules. The photophysical properties of both ICzPy and the Ru(II) assemblies were also examined. Notably, while exhibited a moderately high photoluminescence quantum yield (PLQY), the PLQYs of the arene Ru(II) assemblies decreased sharply to below 2%, likely due to intramolecular photoinduced electron transfer from the donor to the Ru acceptor unit.

Two crystalline tantalum polyselenides, TaSe and TaSe, were synthesized in reactions of the elements at temperatures of 360-380 °C. Crystals of TaSe () were obtained by heating of a mixture of Ta/Se at a molar ratio of 1:6 at 380 °C, while crystals of TaSe () were produced from the same mixture in the presence of either ammonium chloride or ammonium bromide at 360 °C. The crystal structure of TaSe () (space group 2, = 11.680(5), = 11.870(5), = 7.793(4) Å, β = 100.36(2)°, = 2) is a packing of layers which consists of chains with a repeating sequence {-Ta(Se)-Ta(Se)-Ta(Se)-Ta(Se)(Se)-}, where Ta atoms are bridged by di- and triselenide groups, with Ta···Ta distances of 3.15, 3.05, 3.15, and 3.68 Å. These chains are connected in layers by means of Se-Se bonds in the (Se) groups, which form infinite chains of Se atoms. The crystal structure of TaSe () (space group 422, = 9.2876(2), = 12.7133(3) Å, = 2) is a packing of chains {Ta(Se)} and anions (Se), the interatomic distances Ta···Ta in the chains are all 3.18 Å. The experimental observations were supported by DFT calculations of the formation enthalpies of the binary tantalum selenides. The syntheses, structures, and stability of TaSe and TaSe are discussed in this paper.

Herein, we report an improved synthesis of pentafluoroethylated arsanes. Deprotonation of pentafluoroethane by -butyllithium yields the readily available pentafluoroethyllithium, which can be handled at low temperatures. Subsequent reaction with arsenic trichloride affords tris(pentafluoroethyl)arsane in good yields. Control of the degree of substitution at the arsenic center is achieved via the introduction of diethylamino protecting groups. The aminoarsanes AsCl(NEt) and AsCl(NEt) react smoothly with LiCF, enabling the isolation of As(CF)(NEt) and As(CF)(NEt). Cleavage of the diethylamino protecting group with gaseous HCl or HBr affords the corresponding halogenoarsanes. All products represent colorless, volatile liquids, which are characterized by multinuclear NMR spectroscopy. Crystallization of As(CF) as well as As(CF)Cl and As(CF)Br ( = 1,2) is facilitated by crystallization techniques, and the solid-state structures are subsequently determined by X-ray diffraction analysis.

The direct removal of trivalent arsenic (As(III)) from water remains a significant environmental challenge due to its prevalent neutral speciation and low affinity for conventional adsorbents. This study addresses this challenge by systematically engineering the active-site microenvironment of a robust Zr-based metal-organic framework (MOF-808). Through a postsynthetic solvent-assisted ligand exchange (SALE) approach, three distinct amino acids─glycine, asparagine, and histidine─were anchored into the framework to introduce nitrogen-donor sites with varying chemical complexity, creating MOF-808/Gly, MOF-808/Asp, and MOF-808/His. Comprehensive characterization (PXRD, FTIR, XPS, NMR, and BET) confirmed the preservation of the MOF structure and successful functionalization. The adsorption performance revealed a dramatic enhancement in As(III) uptake, with the histidine-functionalized variant (MOF-808/His) achieving a remarkable capacity of 181 mg/g, far surpassing that of the pristine framework. Advanced XPS analysis and adsorption isotherm modeling elucidated the critical role of the amine environment, demonstrating that the imidazole side chain of histidine facilitates superior As(III) binding via synergistic coordination and electrostatic interactions. Our findings establish that side-chain donor strength and pH-dependent protonation are key factors controlling both the thermodynamics and the kinetics of adsorption. This work provides a rational design strategy for creating highly efficient MOF-based adsorbents tailored for the removal of recalcitrant oxyanions like As(III).

Achieving simultaneous room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) in a single material remains a formidable challenge due to the competing nature of intersystem crossing (ISC) and reverse intersystem crossing (RISC). Herein, we report two Ag(I) coordination polymers (CPs): a bromine-free 3D framework, [Ag()(NO)] (CP), and a brominated 1D chain, [Ag()(NO)] (CP). Structural and photophysical analyses reveal that CP exhibits dual RTP/TADF emission with a high photoluminescence quantum yield (PLQY) of 33.6%, whereas CP shows only RTP with a low PLQY of 3.7%. The rigid 3D architecture and absence of heavy atoms in CP facilitate both ISC and RISC processes, enabling efficient exciton utilization. Furthermore, CP demonstrates potential as a temperature-sensitive sensor and a stable luminescent ink for 3D printing. This work highlights a bromine-free structural design strategy for achieving synergistic RTP and TADF emissions in Ag(I) CPs.

We report the synthesis and characterization of Ru mononuclear (), Ru/Pd dinuclear (), and Ru/Ru dinuclear () complexes bearing tetrakis(pyrazol-1-yl)ethene () as a bridging ligand. NMR analyses and single-crystal X-ray crystallography reveal that has a distorted octahedral geometry with symmetry at room temperature and quasi- symmetry upon heating, resulting from the thermally activated motion of . The coordination of to the second metal (Pd or Ru) restricts its motion. In the case of complex , this restriction leads to enhanced emission at room temperature, accompanied by the energy transfer from the Ru unit to Pd.

Density functional theory molecular dynamics simulations were performed to investigate the critical O-O bond formation step mediated by the high-valent Mn-O intermediate in a tetranuclear manganese complex catalyzed water oxidation reaction. The direct coupling mechanism between the oxyl radical and the OH group to form the O-O bond was explored in the octet, 12-tet, and sextet states using an explicit solvation model. The calculated results indicate that the O-O bond formation is kinetically feasible in the octet and sextet states, exhibiting quantitatively similar barriers. In contrast, the O-O bond generation in the 12-tet state is unfavorable. The present study indicates that the O-H bond breaks before the formation of the O-O bond, with a water molecule accepting the released proton. In addition, the DFT-MD simulations incorporating explicit solvation water molecules yielded relatively lower barriers compared to static DFT calculations employing an implicit solvation model. Upon switching from DFT-MD simulations to the static DFT calculations, the barriers increase by 8.0, 15.4, and 15.9 kcal/mol for the octet, 12-tet, and sextet, respectively, highlighting the crucial role of explicit water solvation.

Herein, we address the longstanding challenge of enhancing thermal sensitivity in single-molecule magnets (SMMs) without altering their intrinsic magnetic properties or relying on synthetic modifications. The inherent trade-off between the high symmetry essential for magnetic performance and the low symmetry typically preferred for efficient luminescence has limited progress in conventional thermometric strategies. We demonstrate that magneto-thermometry, based on magnetic relaxation time (τ) and inverse magnetic susceptibility (1/), can serve as a powerful, standalone thermometric tool. An anilato-bridged dinuclear Dy-SMM achieved record high standalone relative magnetothermal sensitivities () of 11.91% K (S) and 9.90% K (S), with S > 1% K spanning 2-100 K, including the critical 2-45 K SMM operating range. To overcome the low luminescence thermometry sensitivity in the complex (S < 0.25% K), we apply multiple linear regression (MLR) to combine optical and magnetic parameters. This multiparametric sensing achieves = 69.58% K (at 15 K) with S > 40% K in the SMM regime, establishing MLR-based opto-magnetic thermometry as a powerful strategy for precise, wide-range temperature sensing in SMMs.

The low activity of metal bridging carbynes has been widely known. Herein, a binuclear heterobimetallic Y/Al "methylidyne" complex underwent nucleophilic addition reactions toward 2, 6-MeCHNC and PhCHCN, respectively yielding monoinsertion products Y[μ-η:η:η-HCC(2,6-MeCH)N](AlMe)(μ-Me) ( = (PhCH)NC(NCHPr-2,6)) () and Y[μ-η:η:η-HCC-(CHPh)N](AlMe)(μ-Me) (). Additionally, complex was treated with PrN═C═NPr (DIC) (5 equiv), obtaining a yttrium complex Y[(AlMe)(NPr)CCHC(NPr)(AlMe)][(NPr)CMe] () featuring an Al-heterocyclic six-membered ring structure and a mixed guanidinate/amidinate yttrium complex Y[(NPr)CMe] (). Complex reacted with CS (2 equiv), leading to the formation of the binuclear yttrium disulfides Y(μ-S)(μ-η:η-S)(AlMe) () through the cleavage of both C═S bonds in CS. Furthermore, a mixed μ-CH/μ-C≡CSiMe yttrium complex [Y(AlMe)](μ-C≡CSiMe)(μ-CH) () was synthesized through the protonolysis of MeSiC≡CH (1 equiv) with complex . Interestingly, the bimetallic alkynyl-bridged yttrium complex [Y(μ-C≡CSiMe)](μ-()-MeSiC═C═C═CSiMe) () was isolated when the MeSiC≡CH (4 equiv) was treated with complex . Notably, in the presence of PhSSPh, complex exhibited distinctive reactivity to CO, undergoing a CO deoxygenative coupling reaction that ultimately yielded a yttrium oxo complex Y(μ-O)(AlMe)(μ-SPh)(μ-C≡CMe) (), and the mixed μ-CH/μ-SPh yttrium complex Y(μ-CH)(μ-SPh)(AlMe) () was identified as a key intermediate in this transformation.

Surface-enhanced Raman scattering (SERS) allows sensitive detection of low-concentration biomolecules by amplifying Raman signals through plasmonic nanoparticles (NPs) such as Au@Ag nanostructures possessing tailorable surface plasmon resonance (SPR). This study presents a seed-mediated growth approach for the synthesis of monodisperse Au@Ag core-shell nanocubes. Their tunable cubic shell thickness () and self-assembly-induced controlled interparticle gaps (IPG) could act as dual optimization for SPR-enabled SERS enhancement. The thickness of the Ag shell is precisely controlled by varying the AgNO concentration. Structural and optical characterizations were conducted by using UV-visible spectroscopy, high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD). The uniform assembly-produced IPG was regulated and achieved by tailoring the concentration of the surfactant CTAB. The SERS performance was evaluated using novel antibodies (aCD47) as a probe molecule, demonstrating that SERS intensity can be effectively optimized by tuning the core-shell composition and IPG. The SERS enhancement factor (EF) of ∼5 × 10 was achieved from Au@Ag nanocubes assembly with and IPG below 10 nm, highlighting strong electromagnetic hotspot formation. The experimentally observed hotspot generation at different and IPG was further backed by numerical simulations using COMSOL Multiphysics.

The development of efficient methane (CH) purification technology from natural gas is crucial to its utilization. Adsorptive separation using porous metal-organic frameworks (MOFs) offers a promising and energy-efficient strategy. Herein, a novel carborane hybrid MOF, Cu-CB-DMTPA, was solvothermally synthesized by using Cu, -CBH-(COOH), and 2,6-dimethyl-,-di(pyridin-4-yl)pyridin-4-amine (DMTPA). This material features electronegative pore surfaces rich in B-H groups and unique one-dimensional (1D) channels with dual pore sizes (large: 6.5 × 4.3 Å; small: 3.4 × 2.8 Å). Gas adsorption studies revealed significantly higher uptake of CH (29.9 cm g) and CH (31.3 cm g) over CH (9.9 cm g) at 298 K and 1.0 bar. Ideal adsorbed solution theory (IAST) selectivity calculations demonstrated outstanding performance for equimolar CH/CH (61.2) and CH/CH (14.4) separations, outperforming many popular materials. The separation mechanism, probed via single-crystal X-ray diffraction (SCXRD) and Grand Canonical Monte Carlo (GCMC) simulations, is attributed to multiple cooperative weak interactions between the framework and hydrocarbons, with stronger binding affinity for larger and more polarizable molecules. Dynamic breakthrough experiments confirmed efficient one-step purification of CH (>99.99% purity) from a CH/CH/CH (85:10:5) mixture at 298 K, achieving a high CH productivity of 81.53 L kg. Cu-CB-DMTPA also maintains excellent recyclability and humidity resistance, highlighting its potential for industrial natural gas upgrading.

The development of efficient and sustainable heterogeneous catalysts remains central to the advancement of green oxidation chemistry. Herein, we report a Ni-salphen-derived metalated porous organic polymer (), synthesized via a simple Friedel-Crafts alkylation strategy that integrates atomically dispersed Ni-NO active sites into a robust carbazole-linked framework. A combination of 2D solid-state C-H double cross-polarization (CP) correlation NMR, XPS, synchrotron-based XAS, and electron microscopy techniques confirmed the structural integrity, amorphous porous architecture, and uniform dispersion of Ni centers. Electronic analyses revealed reduced surface electron density at the Ni sites, enhancing their Lewis acidity and catalytic reactivity. demonstrated exceptional performance in the aerobic allylic oxidation of cyclohexene under ambient conditions, affording complete conversion with high selectivity and remarkable recyclability over multiple cycles without detectable Ni leaching. Complementary DFT calculations unveiled favorable charge transfer and energetically viable pathways consistent with experimental observations. This study establishes surface electron density as a powerful activity descriptor and underscores the promise of rationally engineered metalated porous polymers for sustainable oxidation catalysis.

Herein, we present a theoretical framework to uncover the crucial roles of interlayer magnetic exchange of two-dimensional hexaaminobenzene (HAB)-based metal-organic frameworks (TM-HAB) catalysts on electrocatalytic oxygen reduction reaction (ORR) performance. Through multistage screening, monolayer Fe-HAB-I and Co-HAB-I were identified as optimal for 4e and 2e ORR pathways, respectively. Grand Canonical Density Functional Theory (GC-DFT) and Monte Carlo simulations revealed monolayer Co-HAB-I prefers to a 2e ORR with an onset potential of 0.95 V vs RHE under alkaline conditions, while Fe-HAB-I exhibits 4e ORR activity at the onset potential of 0.73 V vs RHE in acidic environments. For experimentally relevant multilayer systems, GC-DFT calculation of bilayer Fe-HAB-II highlights the critical role of interlayer magnetic coupling: the ferromagnetic (FM) state demonstrates a markedly higher onset potential than the antiferromagnetic (AFM) state at pH = 13. Notably, Fe-HAB-II in the FM state achieves a theoretical onset potential of 1.17 V vs RHE, closely aligning with experimental observations (1.02 V vs RHE), thereby validating the crucial roles of interlayer spin exchange on ORR property. This work underscores the pivotal influence of interlayer magnetic interactions in optimizing two-dimensional electrocatalysts for ORR.

We report herein the synthesis and optical properties of a lanthanide chalcogenide scintillator, CeCsSiS, which crystallizes in the orthorhombic space group and adopts a two-dimensional layered structure. CeCsSiS exhibits ultrabroadband emission spanning 400-950 nm with a record full width at half-maximum (fwhm) of 207.3 nm among Ce-based inorganic emitters. The emission originates from the combined contributions of the Ce-5d → 4f transition and Ce-5d → S-3p charge-transfer transitions. The material shows a high photoluminescence quantum yield of 51.6%, a fast decay time of 26.4 ns, strong X-ray radioluminescence, and excellent radiation and moisture stability, demonstrating promise for robust X-ray detection.

Here, we demonstrate the design and synthesis of a dynamic tubular nanostructure with photoactive properties through hybrid supramolecular hierarchical assembly. The key to the successful construction of discrete single nanotubes lies in the unique K-shaped viologen-BODIPY-based precursor (), which enables geometric sequence control via silver(I) linear coordination and cucurbit[10]uril-mediated host-guest interactions in aqueous solution. Notably, the resulting nanotubes exhibit dynamic assembly behavior and enhanced photocatalytic activity in aqueous solution due to the photosensitivity of BODIPY within the rigid nanotube framework. This study provide new insights into the fabrication of dynamic functional nanotubes based on metal coordination and macrocycle-driven host-guest assemblies.

(Co)doping luminescent center(s) in a host is a universal strategy to photoluminescence (PL) modulations for extensive applications, yet its mechanism and interactions between structure and behavior in many phosphors remain ambiguous. Herein, via a facile sol-gel reaction method, differently tendentious occupations of Ce in distinct crystallographic sites of KYSiO (KYS) lead to tunable PL in between blue and bluish-green under diverse excitations with high quantum efficiency. The generation of wide trap energy levels originating from heterovalent substitution Tb → K could entrust Tb as both PL and long-persistent PL (LPL) centers in green. Due to temperature-dependent filling/releasing rates of captured carriers, strong thermal-induced LPL could be obtained in KYS: Tb. By codoping Ce/Tb in KYS, multimode anticounterfeiting and information storage/encryption of KYS: Ce/Tb are realized with high security level via a screen printing technique. Because Ce and Tb possess different temperature-dependent quenching behaviors, optical temperature sensing is achieved with high absolute/relative sensitivity. To further enhance the KYS: Ce/Tb performance, trap depth engineering via equivalent substitution Gd → Y is further executed. The colorimetric/photometric analyses here provide new insights into designing novel stable and single-phased phosphor for applications in advanced anticounterfeiting technology and optical thermometry.

This study focuses on the synthesis and characterization of a symmetrical bidentate Schiff base ligand, '-bis(4-bromobenzylidene)-2,2-dimethylpropane-1,3-diamine, and its Cu(I) complexes with halide ligands (Cl, Br, and I). The ligand and complexes were characterized using FT-IR, NMR spectroscopy, and elemental analysis. X-ray crystallography revealed distorted trigonal planar geometries around the Cu(I) center, supported by weak intermolecular interactions like C-H···X (X = Cl, Br) and C-H···π stacking. Electrochemical analysis at a scan rate of 25 mV/s indicated that the Cu(II)/Cu(I) redox process is electrochemically irreversible. Catalytic efficiency was evaluated in the synthesis of dihydro-1-imidazoles and tetrahydropyrimidines. Mechanistic DFT (density functional theory) studies proposed a favorable 4-coordinate pathway. The present study underscores the structural versatility and catalytic efficiency of Cu(I) Schiff-base complexes, establishing a framework for their potential utilization in pharmaceutical synthesis and coordination chemistry.

Three new red-emitting cationic cyclometalated iridium complexes with formula [Ir(C^N)(N^N)][ClO] (C^N = substituted quinoxaline[X-dpqx], N^N = 2-(1-benzyl-1H-benzo[]imidazole-2-yl) quinoline, namely: IrQ1, 2, 3, where = H, Cl, and OCH, respectively) have been synthesized for application as an emitter in light-emitting electrochemical cells (LECs). The (quasi-) reversible redox behavior of the complexes confirmed their electrochemical stability as an important feature of emitters for achieving efficient LECs. Complexes IrQ1, 2, and 3 exhibit intense emissions in the red region (622-645 nm), with photoluminescence quantum yields (PLQYs) of 7, 18, and 3%, respectively, in a CHCl solution. Furthermore, the neat-film PL of the complexes showed a significant red shift in emission by about 55-80 nm. To investigate the stability of the complexes against water exchange reactions during LEC operation, for the first time, their electrocatalytic activity for the water splitting reaction was examined, and their high inertness, especially complex IrQ2, was confirmed. With the ligand substitution strategy, an efficient and stable LEC with IrQ2 as the emitter was fabricated, which illustrated a deep-red emission (661 nm) with a luminance of 19 cdm and an external quantum efficiency (EQE) of 0.95%. The obtained EQE value is several times higher than that of similar diphenylquinoxaline/Ir-based LECs.

The widespread application of direct methanol fuel cells (DMFCs) is limited by the sluggish kinetics of the anodic reaction, the high cost of catalysts, and their susceptibility to poisoning. Pd-based catalysts are among the most promising anode materials for DMFCs; however, their sluggish methanol oxidation reaction (MOR) kinetics and poisoning resistance require further enhancement to meet practical demands. In this study, we accurately regulate the electronic structure of Pd by synthesizing a series of Pd-Cu/C alloy catalysts with precisely controlled Pd/Cu atomic ratios, thereby realizing the efficient and poison-resistant electrocatalyst for MOR. Theoretical calculations reveal that the electronic structure of Pd is modulated by controlling the incorporation of Cu, which weakens CO* adsorption at Pd sites and enhances OH* affinity at Cu sites, accelerating the oxidation and removal of CO* on Pd sites, boosting the methanol oxidation performance of PdCu alloys. The PdCu/C catalyst (Pd:Cu = 1:1) exhibited a remarkable mass activity of 1276.82 mA·mg, 1.86 times higher than Pd/C (686.95 mA·mg), and retained 61.3% of its activity in durability tests, surpassing Pd/C (48.4%). CO stripping tests further confirmed its superior CO tolerance. This work provides a pathway for developing high-performance, CO-tolerant anode catalysts suitable for advanced fuel cells.

In the Cu-S family, it is of great importance to advance the phase control of the CuS nanocrystals (NCs) for a given application. In this regard, recently, a large library of sulfur precursors have been explored in the colloidal syntheses. Nevertheless, the links between their conversion pathways and the phase of the resulting CuS NCs are rarely established. Herein, we unravel the conversion pathways of thiourea (TU) heated in an oleylamine (OAm) solvent and identify the reactive sulfur species. The pyrolysis of primary TU produced intermediate CS, and it converted into ultimate reactive sulfur species HS gas and ,-disubstituted TU via the reaction with OAm. These two sulfur species are linked to the phase determination of cubic-phase digenite CuS NCs and hexagonal-phase djurleite CuS NCs, respectively. Furthermore, the above TU-OAm solutions are utilized to the polymorphic synthesis of CuS-derivative Cu-In-S and Cu-Sn-S NCs with a cubic zinc blende phase and a hexagonal wurtzite phase. Therefore, our findings in the present study suggest an urgency on unraveling the conversion pathways of primary sulfur precursors in organic solvents, holding great promise in the synthesis of other metal sulfides with phase-related functionalities.

A family of stable, crystalline half-parent vinyl-tetrylenes L(CH)E: (-; L = {[RPCHSi(Pr)](Dipp)N}; Dipp = 2,6-PrCH; R = Ph, Cy) is reported, accessed via a straightforward salt-metathesis pathway, and their electronic properties and initial reactivity explored. All compounds display downfield-shifted signals in both the H and C NMR spectra for their [CH] ligand, being most extreme for Pb due to relativistic effects. UV-vis spectra of compounds - reveal bathochromic shifts relative to the halo-tetrylene derivatives (i.e., LEX; X = Cl, Br), due to stabilization of the LUMO through overlap of the E-centered -orbital and the π*-orbital of the [CH] unit. Vinyl group elimination is demonstrated in the plumbylene system, whereby reaction with the strong electrophile [PhC][BAr] (Ar = 3,5-(CF)CH) afforded low-coordinate Pb cation , stabilized by the chelating ligand and secondary interactions with the weakly coordinating BAr anion. Finally, addition of vinyl-germylenes () to Ni synthons enabled the synthesis of mono- and bis(vinylgermylene)-nickel(0) complexes and , whereby binding occurs through the tetryl centers and not the vinyl fragment, representing the first examples of vinyl-tetrylene coordination complexes reported to date.