Metal-organic framework containing Co(μ-OH)-based kagomé layers showing long-range weak ferromagnetic ordering.

The compounds Co(OH)(5-cnapp)(HO) (1) and Co(OH)(4-cnapp)(HO)·12HO (2) obtained using positionally isomeric phosphonic acids (5-/4-cnappH) have 3D framework structures. Compound 1 contains a distorted Co(μ-OH)-based kagomé layer and shows long-range weak ferromagnetic ordering below 30 K without significant spin frustration.

All-component-active metal-organic frameworks for tailored chemoradiotherapy of self-defensive tumors.

Radiotherapy is a widely used clinical treatment for locoregional cancers, but it still faces radiation resistance arising from abundant glutathione (GSH) and DNA damage repair (DDR). To overcome these self-defense pathways, various radiosensitizers have often been integrated with pharmaceutical agents, forming hybridized carriers for combination therapy. Herein, an all-component-active metal-organic framework (aaMOF), composed of chemotherapeutic thioguanine as a linker and copper iodide as nodes, is rationally designed for tailored chemoradiotherapy against tumor self-defense pathways.

Synergistic Photoredox and High-Spin Cobalt Cluster Dual Heterogeneous Catalysis: Visible-Light-Driven C(sp)-H Bond Functionalization.

We report visible-light-driven C(sp)-H functionalization of indoles with naphthoquinone using a dual photocatalytic system of Eosin Y and a high-spin cobalt cluster. This one-pot transformation provides efficient access to a variety of pharmaceutically relevant heterocycles from readily available indoles under chemical oxidant-free and environmentally benign conditions. The reaction scope is further extended to the cyclization of aromatic amines, yielding amination products in moderate to good yields.

A thermally and photoresponsive luminescent single-molecule magnet based on dysprosium-anthracene: effect of temperature on anthracene photocycloaddition.

Stimuli-responsive lanthanide-based single-molecule magnets (Ln-SMMs) are attractive for their potential in information storage, sensors and molecular devices. However, challenges remain in synergistically tuning the magnetic and optical properties of Ln-SMMs at the same temperature. Herein, we report a mononuclear dysprosium complex containing anthracene units, namely [Dy(SeCN)(NO)(depma)(4-hpy)] (1DySeCN) (depma = 9-diethylphosphonomethylanthracene, 4-hpy = 4-hydroxypyridine).

Optimal Reference Genes for Gene Expression Analysis of Overmating Stress-Induced Aging and Natural Aging in Male .

Functional gene expression is closely linked to an organism's physiology and can be quantified using Real-Time Quantitative Reverse Transcription PCR (RT-qPCR). However, the stability of reference gene expression is not absolute, which may impact the accuracy of RT-qPCR results. In this study, we evaluated the suitability of nine genes including receptor for activated protein kinase c1 (), ribosomal protein L6 (), ribosomal protein L9 (), ribosomal protein S2 (), ribosomal protein S18 (), ribosomal protein lateral stalk subunit P0 (), eukaryotic translation elongation factor 1β (), eukaryotic translation initiation factor 4a (), eukaryotic translation initiation factor 5a () analyzed from RNA sequencing (RNA-Seq) data in addition to three genes including eukaryotic elongation factor 1α (), β-actin (), and glyceraldehyde 3-phosphate dehydrogenase () selected from the literature to obtain the best internal controls in the RT-qPCR analysis of under overmating stress and natural aging.

Lanthanide-Diphosphonate Frameworks Containing Dianthracene: Isolation of Metastable Intermediates and Lanthanide-Dependent UV and X-ray Light-Responsive Properties.

Capturing kinetic intermediates is crucial for understanding the formation mechanism of metal-organic frameworks (MOFs), but it is particularly challenging for metal phosphonate frameworks. Here, we employ a modulator-based strategy to control the crystallization of MOFs. By adding the chelating ligand shikimic acid, we obtained three-dimensional (3D) lanthanide-diphosphonate frameworks, [Ln(ampH)(HO)]·4HO (, = 6, Ln = Sm, Eu, Gd, Tb, Ho; = 4, Ln = Er), where ampH is prephotodimerized 9-anthracenemethylphosphonic acid.

Polychromatic Electrochemiluminescence Imaging of Single Heteroligand Metal-Organic Crystals.

Conventional polychromatic electrochemiluminescence (ECL) imaging is realized with the several separated luminophores at the different potentials. In this study, an emerging polychromatic ECL imaging system was constructed based on single heteroligand metal-organic framework (MOF) crystals as nanoemitters through an intrareticular energy transfer process. The heteroligand MOF crystals, named h-NJU-241, were coassembled of meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) with 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy) ligand using benzoic acid catalyst with coordination ability, leading to the conjugated spacing of 0.

Homochiral layered indium phosphonates: solvent modulation of morphology and chiral discrimination adsorption.

Assembling chiral coordination polymers into nano/microflower structures may improve their performance in applications such as chiral recognition and separation. In this study, we chose a chiral metal phosphonate system, , In(NO)/-, -pempH [pempH = (1-phenylethylamino)methylphosphonic acid], and carried out systematic work on the self-assembly of this system in different alcohol/HO mixed solvents under solvothermal conditions. Enantiomeric compounds -, -[In(pempH)(μ-OH)(HO)](NO) (R-, S-1) were obtained showing dense layered structures, but their morphologies varied with alcohol solvent.

Hollow Superhelices Based on Chiral Europium Coordination Polymers.

The construction of helical nanotubes based on chiral coordination polymers (CPs) is an intriguing but challenging task, which is important for the development of functional materials that combine macroscopic chirality with tube-related properties. Here, we selected a chiral europium phosphonate system, e. g.

Nitrate-Anion-Induced Formation of a 2D Metal-Organic Framework with an Unconventional Kagomé Lattice Exhibiting Methanol-Mediated Ketone Catalysis.

Metal-organic frameworks (MOFs) with kagomé lattice are attractive for their unique physical and chemical properties, but little attention has been paid to their catalytic properties. Herein, we report a 2D MOF based on a phosphonato-amino-carboxylate ligand (NaHL), i. e.

Lanthanide-Sensitized Upconversion Iridium Complex via Triplet Energy Transfer.

Cyclometalated iridium (Ir) complexes demonstrate impressive capabilities across a range of fields, including biology and photocatalysis, due to their tunable optical characteristics and structure flexibility. However, generating upconversion luminescence of Ir complexes under near-infrared light excitation is challenging. Herein, by employing lanthanide-doped upconversion nanoparticles (UCNPs) as the sensitizer, a new strategy is demonstrated to gain upconversion luminescence of Ir complexes via triplet energy transfer.

Ternary Eutectic Electrolyte-Assisted Formation and Dynamic Breathing Effect of the Solid-Electrolyte Interphase for High-Stability Aqueous Magnesium-Ion Full Batteries.

Aqueous rechargeable magnesium batteries hold immense potential for intrinsically safe, cost-effective, and sustainable energy storage. However, their viability is constrained by a narrow voltage range and suboptimal compatibility between the electrolyte and electrodes. Herein, we introduce an innovative ternary deep eutectic Mg-ion electrolyte composed of MgCl·6HO, acetamide, and urea in a precisely balanced 1:1:7 molar ratio.

Solvent modulation of the morphology of homochiral gadolinium coordination polymers and its impact on circularly polarized luminescence.

Studying the effect of morphology on the circularly polarized luminescence (CPL) of chiral molecular materials is important for the development of CPL-active materials for applications. Herein, we report that the morphology of Gd(NO)/-,-AnempH [AnempH = (1-anthrylethylamino)methylphosphonic acid] assemblies can be controlled by solvent modulation to form spiral bundles Gd(-,-AnempH)·2HO (R-,S-1), crystals Gd(-,-AnempH)·2HO (R-,S-2) and spindle-shaped particles Gd(-,-AnempH)·3HO·0.5DMF (R-,S-3) with similar chain structures.

Enhancing the Circularly Polarized Luminescence of Europium Coordination Polymers by Doping a Chromophore Ligand into Superhelices.

Lanthanide-based molecular materials showing efficient circularly polarized luminescence (CPL) activity with a high quantum yield are attractive due to their potential applications in data storage, optical sensors, and 3D displays. Herein we present an innovative method to achieve enhanced CPL activity and a high quantum yield by doping a chromophore ligand into a coordination polymer superhelix. A series of homochiral europium(III) phosphonates with a helical morphology were prepared with the molecular formula -, -[Eu(cyampH)(nempH)]·3HO (/, = 0-5%).

Macroscopic Helical Assembly of One-Dimensional Coordination Polymers: Helicity Inversion Triggered by Solvent Isomerism.

Assembling macroscopic helices with controllable chirality and understanding their formation mechanism are highly desirable but challenging tasks for artificial systems, especially coordination polymers. Here, we utilize solvents as an effective tool to induce the formation of macroscopic helices of chiral coordination polymers (CPs) and manipulate their helical sense. We chose the Ni/-,-BrpempH system with a one-dimensional tubular structure, where -,-BrpempH stands for -,-(1-(4-bromophenyl)ethylaminomethylphosphonic acid).

Layered lanthanide phosphonates Ln(2-qpH)(SO)(HO) (Ln = La, Ce, Pr, Nd, Sm): polymorphism and magnetic properties.

Polymorphic layered lanthanide coordination polymers provide opportunities to study the effect of intralayer and interlayer interactions on their magnetic dynamics. Herein we report a series of layered lanthanide phosphonates, namely, α-Ln(2-qpH)(SO)(HO) (Ln = Sm) (α-Ln), β-Ln(2-qpH)(SO)(HO) (Ln = Pr, Nd, Sm) (β-Ln) and γ-Ln(2-qpH)(SO)(HO) (Ln = La, Ce, Pr, Nd, Sm) (γ-Ln) (2-qpH = 2-quinolinephosphonic acid), which crystallize in monoclinic 2/ (α-Ln), triclinic 1̄ (β-Ln) and orthorhombic (γ-Ln) space groups, respectively. The structural differences between the β- and γ-phases lie not only in the intralayer but also in the interlayer.

Octahedral lanthanide clusters containing a central PO anion: structural, luminescent, magnetic and relaxometric properties.

Lanthanide clusters with good stability and intriguing physical properties are attractive in many fields. By reacting 9-anthracenylphosphonic acid (AnPOH) and lanthanide nitrates under solvothermal conditions, we obtained a series of hexanuclear lanthanide phosphonate cages [HO][Ln(PO)(AnPO)(DMF)]·2DMF·HO (Ln6, Ln = Nd, Eu, Gd, Dy, Ho, Er, Yb). Within the cluster, the six Ln atoms form an octahedron and its eight faces are covered by phosphonate groups.

A Self-Templated Design Approach toward Multivariate Metal-Organic Frameworks for Enhanced Oxygen Evolution.

Multivariate metal-organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M-NiMOF (M = Co, Cu) through a simple self-templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu-NiMOFs demonstrate the improved intrinsic electrocatalytic activity.

pH and Salt-Assisted Macroscopic Chirality Inversion of Gadolinium Coordination Polymer.

The precise adjustment of handedness of helical architectures is important to regulate their functions. Macroscopic chirality inversion has been achieved in organic supramolecular systems by pH, metal ions, solvents, chiral and non-chiral additives, temperature, and light, but rarely in coordination polymers (CPs). In particular, salt-assisted macroscopic chirality inversion has not been reported.

X-Ray Triggered Coordination-Bond Breakage in Dysprosium-Organic Framework and its Impact on Magnetic Properties.

Photosensitive lanthanide-based single-molecule magnets (Ln-SMM) are very attractive for their potential applications in information storage, switching, and sensors. However, the light-driven structural transformation in Ln-SMMs hardly changes the coordination number of the lanthanide ion. Herein, for the first time it is reported that X-ray (λ=0.

Polymorphism modulates photoluminescence and magnetic dynamics of mononuclear dysprosium-anthracene complexes.

Complexes α-Dy(depma)Cl (α-DyCl), β-Dy(depma)Cl (β-DyCl) and β-Dy(depma)Br (β-DyBr) (depma = 9-diethylphosphono-methylanthracene) are reported. α-DyCl and β-DyCl are polymorphs showing distinct magnetic dynamics with energy barriers of 32.3 K and 66.

Photoresponsive proton conduction in Zr-based metal-organic frameworks using the photothermal effect.

A highly stable and porous MOF [Zr(HTPPP)(OH/F)]·HO (1) containing a metal-free porphyrin-phosphonate ligand is reported. It shows high proton conductivity of 1.2 × 10 S·cm at 25 °C and 95% RH, a photothermal effect over a wide spectral range from UV-vis to NIR, and photo-enhanced and switchable proton conductivity.

Layered Uranyl Phosphonates Encapsulating Co(II)/Mn(II)/Zn(II) Ions: Exfoliation into Nanosheets and Its Impact on Magnetic and Luminescent Properties.

Layered heterometallic 5f-3d uranyl phosphonates can exhibit unique luminescent and/or magnetic properties, but the fabrication and properties of their 2D counterparts have not been investigated. Herein we report three heterobimetallic uranyl phosphonates, namely, [(UO ) M(2-pmbH) (H O) ] ⋅ 2H O [MU, M=Co(II), CoU; Mn(II), MnU; Zn(II), ZnU; 2-pmbH =2-(phosphonomethyl)benzoic acid]. They are isostructural and display two-dimensional layered structures where the M(II) centers are encapsulated inside the windows generated by the diamagnetic uranyl phosphonate layer.

Uranyl phosphonates: crystalline materials and nanosheets for temperature sensing.

Ultrathin nanosheets of luminescent metal-organic frameworks or coordination polymers have been widely used for sensing ions, solvents and biomolecules but, as far as we are aware, not yet used for temperature sensing. Herein we report two luminescent uranyl phosphonates based on 2-(phosphonomethyl)benzoic acid (2-pmbH), namely (UO)(2-pmbH) (1) and (HO)[(UO)(2-pmb)(2-pmbH)] (2). The former has a supramolecular layer structure, composed of chains of corner-sharing {UO} octahedra and {POC} tetrahedra which are connected by hydrogen bonds between phosphonate and carboxylic groups.