Using two modified pyridine-triazole ligands (bis(5-(4-methylpyridin-2-yl)-4H-1,2,4-triazol-3-yl)methane, abbreviated as H2bmptm, and bis(5-(pyrimidin-2-yl)-4H-1,2,4-triazol-3-yl)methane, abbreviated as H2bpmtm), three {Gd6(OH)6} clusters were solvo-thermally synthesized: [Gd6(OH)6(Cl)4(bmptm)4(DMF)4] (1), [Gd6 (OH)6(NO3)4(bmptm)4(DMF)4] (2) and [Gd6(OH)6(OC2H5)2(Cl)2(bpmtm)4(H2O)4]center dot 7C2H5OH (3). 1-3 exhibits similar structural features, comprising a {Gd6(OH)6} core formed by four edge-sharing Gd3 triangular units linked via mu 3-OH-bonds, along with modified bmptm/bpmtm ligands, as well as coordinated anion/solvents. Taking 1 for example to study the solution assembly process of these [Gd6] complexes. The stepwise formation of Gd1(bmptm)1 -> (Gd2(bmptm)1 + Gd3(bmptm)1 + Gd1(bmptm)2) -> Gd6(bmptm)4 had been tracked by the time-dependent mass spectrometry. Magnetic properties showed that 1 3 displayed significant magnetocaloric effects (MCE) with the-Delta Smvalues of 23.27-24.64 J K-1 kg-1. Additionally, the studies on their magnetic resonance imaging (MRI) contrast give longitudinal relaxation rates of r1 (4.19-6.68 mM-1s-1), under the 3T magnetic field.

Facilitated by the tert-butyl substituent in a C2-symmetric bis(hydrazone), along with the incorporation of 3d ions, oxalate, carbonate, and sodium ions, a homononanuclear dysprosium ring [Dy9(L1)3(μ3-O)4(μ3-AcO)3(μ2-AcO)6 (μ2-COO)3(DMF)3]·3DMF·1MeOH·6H2O (Dy9) and a heterooctaoctacontanuclear dysprosium-zinc-sodium ring [Dy48Zn24Na16(L2)24(μ6-C2O4)8(μ4-C2O4)18(μ4-CO3)8(μ4-AcO)34(μ4-COO)16(DMF)10(H2O)28]·2Cl·46DMF·38MeCN·82H2O (Dy48Zn24Na16) were synthesized. Compounds Dy9 and Dy48Zn24Na16 exhibit distinct single- and triple-stranded cyclic topologies, in which the bis(hydrazone) ligands L1 and L2 adopt different conformations and exhibit distinct metal coordination modes. While 12 acetate molecules serve as terminal coligands occupying the remaining coordination sites in assembly Dy9, hexacosuple-C2O42-, octuple-CO32- and triacontatetraple-AcO- bridges act as mixed oxoanion templates to form Dy48Zn24Na16 by linking hexanuclear Dy6Zn3Na2(L2)3 building blocks. Sixteen sodium ions act as a tertiary template, filling the internal void of the latter structure. Furthermore, it was observed that the structural modifications largely influence the zero-field magnetic relaxation behavior. This work presents a new approach for constructing C2O42--, CO32-- and AcO-- bridged heterometallic metallosupramolecular rings through the deliberate addition of oxalate, carbonate and acetate for magnetic dynamic studies.

In recent research, an atomically precise Cu(II) complex (Cu8) consisting of eight copper atoms has been successfully synthesized. This complex exhibits a unique capability to catalyze a Fenton-like reaction within the tumor microenvironment (TME), which is characterized by overexpressed hydrogen peroxide. The Cu(II) complex Cu8 exploits this condition to generate highly cytotoxic hydroxyl radicals. These radicals are extremely effective in inducing programmed cell death or apoptosis in HeLa cells, a type of cervical cancer cell, and additionally cause significant damage to the mitochondria (the powerhouses of the cell). Due to these properties, the complex functions as a potent chemodynamic therapy (CDT) agent, demonstrating promising antitumor potential. The precise coordination of the [Ph2PO2]- ligand within the complex is critical to its effectiveness in catalyzing the Fenton-like reaction, thereby enabling its therapeutic application in chemodynamic therapy.

A robust Mn(ii) MOF with high thermal stability and chemical stability was prepared as an effective catalyst for thioether oxidation, cyanosilylation and Knoevenagel condensation with recycling runs.

Molecular cages are generally divided into covalent organic cages (COCs) and metal-organic cages (MOCs), which are formed through the self-assembly of organic or metal-organic building blocks. In this review, an...

In this paper, a {Zn6}-HOFs was synthesized successfully, the striking feature of it is that the arrangement allows the formation of the three-dimensional super-molecule Metalo-hydrogen-bonded organic frameworks. Subsequently, we revealed the possible assembly process of {Zn6}-HOFs. The {Zn6}-HOFs can be used as fluorescent sensor to detect Cu2+ and Cr2O72- with a limit of detection (LOD) of 21 nm and 0.17 mu M, respectively.

The controllable construction and assembly of sophisticated aggregates with specific metal centers or skeletons has become a hot topic in coordination chemistry. However, monitoring the assembly process remains a significant challenge. In this paper, the stepwise formation of a {Co9} grid with a [3 x 3] skeleton was monitored by electrospray ionization mass spectrometry (ESI-MS). Based on the observed intermediates, a possible formation pathway was proposed as follows: [Co2L2] -> [Co3L2] -> [Co4L3] -> [Co5L3] -> [Co6L4] -> [Co7L4] -> [Co8L5] -> [Co9L6]. From the {Co9} grid precursor, homometallic {Co9Co2} and heterometallic {Co9Cd2} clusters with similar skeletons were prepared from the postsynthetic modification strategy when dotted with para-magnetic Co2+ ions and dia-magnetic Cd2+ ions. Furthermore, the detailed structures of {Co9Co2} and {Co9Cd2} were characterized by single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy coupled (SEM) with energy-dispersive X-ray spectroscopy (EDS), and ESI-MS. Compared with {Co9} precursor, the magnetic signal of {Co9Co2} was enhanced after postmodificated with paramagnetic Co(II) ions, but in {Co 9 Cd 2 }, which keep silence upon the introducing of diamagnetic Cd(II) ions.

Four lanthanide (Ln = Tb, Eu, Gd, Dy) complexes were solvothermally synthesized from a bitriazole pyridine dicarboxylic acid ligand (H4btpa) and Ln2O3 in a water/ethyl acetate mixed solvent. The luminescence behavior of the Tb4 and Eu4 complexes enables the selective detection of metronidazole (an antibiotic), with detection limits of 10.29 and 25.46 nM, as well as the determination of Co(II) ions, with detection limits of 30.8 and 125.6 nM, respectively. The mixed Tb4-Co and Eu4-Co systems were further used to detect DPA, with detection limits (202.8 and 512.5 nM, respectively) superior to that of the Ln4 system. The magnetic properties of Gd4 indicated magnetocaloric effects, with a maximum-Delta Sm value of 32.01 J K-1 kg-1, while Dy4 exhibited frequency-dependent behavior.

In recent years, in addition to the widely studied Cu-based nanomaterials for chemodynamic therapy (CDT), discrete Cu CDT complexes have received much attention due to their atom-precise structural characteristics and their efficient anticancer treatment. Metal-organic cage (MOCs) a class of highly ordered discrete supramolecular complexes with well-defined cavities and multiple metal catalytic centers, could be a good candidate for CDT research. Herein, a Cu10L8 metal-organic cage (Cu10L8) with exchangeable anions has been synthesized by using a flexible ligand of H2L (1H-imidazole-4-carbaldehyde-1,3-diaminopropan-2-ol) and characterized. Meanwhile, Cu10L8 can generate a large amount of highly toxic hydroxyl radicals (center dot OH) through Fenton-like reaction, thereby promoting mitochondrial oxidative stress in the mitochondria and ultimately leading to cell apoptosis. Cu10L8 exhibited excellent antitumor activity against SK-OV-3 cells and promising CDT effect. We believe that Cu10L8 can enrich the selection of atomic-precise CDT metal complexes, and then provide new candidates for the development of CDT agents with cage-like structure.

Monitoring the assembly process of coordination polymers (CPs) is crucial for elucidating the assembly mechanism and developing new CPs with well-defined structures and functions. In this paper, a one-dimensional coordination polymer of {Mn2-1D} have been constructed from discrete {Mn4} clusters, along with thermal dehydration. The thermotropic dimension augmentation process was monitored via single crystal/powder X-ray diffraction (SC/P-XRD), infrared spectroscopy and Raman spectroscopy. Additionally the enhanced magneto-thermal properties of CPs were investigated. During the dimension augmentation, the magnetic entropy change values increased from 26.92 J K-1kg-1 in {Mn4} to 36.78 J K-1kg-1 in {Mn2-1D} (T = 2 K, Delta H = 7 T).

Controllable synthesis of sophisticated aggregations has attracted wide attention from scientists. In this work, homo- and heterometallic {CoIIICoII 12MII 6} (M = CoII/CdII) aggregates with similar skeletons, composed of two [Co3M3(dpbt)3] peripheries and a central [Co7(OH)8] vertex-fused double-cubane, were constructed from prefabricated {Co14} clusters and characterized by single-crystal X-ray diffraction and XPS, ICP-MS, SEM (EDX), and so on. And then, the structure and magnetic differences of them had been further analyzed under dotted with paramagnetic CoII ions and/or diamagnetic CdII ions. Interestingly, the spin canting behavior in {Co III Co II 18 } was suppressed in {Co III Co II 12 Cd II 6 }, upon the introducing of CdII ions.

In this study, two octa-nuclear lanthanide complexes consisting of a templated Ln(8) (Ln = Tb, Dy) cluster and a '' 4 + 4 '' type Schiff-base covalent organic macrocycle, named Ln(8)L(4+4), were constructed successfully. The stepwise solution assembly process of Tb8L4+4 from the initial organic subcomponents and metal templates was tracked as Tb1L1+2 -> Tb2L1+2 -> Tb3L1+2 -> Tb3L2+2 -> Tb4L2+2 -> Tb4L3+2 -> Tb5L3+2 -> Tb6L3+2 -> Tb8L4+4, through ESI-MS technology. Interestingly, Tb8L4+4 can be used as a sensitive and selective fluorescence-sensing material to determine the level of dipicolinic acid (DPA), and Dy8L4+4 has the characteristics of a single molecule magnet behavior.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

It is important to develop sensors that can be easily fabricated for the detection of harmful industrial wastes and nitroaromatic explosives to reduce the risks to human health and protect the environment. We report a new luminescent metal-organic framework (MOF), [Zn-5(mu(3)-OH)(2)(TDA)(4)(4,4 '-bpt)(2)]n (1), (4,4 '-bpt = 1H-3,5-bis-(4-pyridyl)-1,2,4-triazole, H(2)TDA = thiophene-2,5-dicarboxylic acid), which was synthesized under solvothermal conditions and characterized using the PXRD, IR, TG, ICP-MS, mapping, and PL spectroscopic techniques. The {Zn-5} MOF of (1) with Zn-5 cluster as the node, and 4,4 '-bpt and TDA(2-) as linkers, exhibited excellent thermal and chemical stabilities. Furthermore, 1 can serve as a sensitive and recyclable luminescent probe for the detection of Ag+, Cr2O72-, and TNP with detection limits of 5.96, 4.34, and 1.59 mu M, respectively.

Using the polydentate ligand of H4L with the CoII ion, a triangular prism-type nine-nucleus cluster [Co9(L)3(CH2OCH2OH)6]·3.5H2O ({Co9}-Eg, H4L = 6,6'-(1H,1'H-[3,3'-bi(1,2,4-triazole)]-5,5'-diyl)dipicolinic acid) was constructed. Ion fragmentation during the formation of the {Co9}-Eg cluster was tracked using time-dependent electrospray ionization mass spectrometry. In addition, we proposed two possible formation processes (i) H4L → CoL → Co2L → Co6L3 → Co7L3 → Co9L3 and (ii) H4L → CoL → Co2L → Co3L → Co5L2 → Co7L3 → Co9L3. Magnetic studies show that {Co9}-Eg exhibits slow relaxation under a static zero field at low temperature, which is the main characteristic of single molecule magnets (SMMs).

Doxorubicin (DOX) is an anthraquinone drug used for the efficient treatment of a variety of tumors in human beings. Unfortunately, its poor biodegradability causes incomplete metabolism in the body. Therefore, it is of great significance to synthesize a sensitive and selective material for DOX detection. In this paper, we report a water-soluble Tb12 cluster and track its step-by-step formation (L → Tb1L1 → Tb2L1 → Tb2L2 → Tb3L2 → Tb4L2 → Tb12L6). Tb12 can be used to determine the presence of DOX, which quenches the luminescence of the Tb12 aqueous solution, and the detection limit can reach 13 nM (KSV = 8.7 × 105 M-1). Tb12 has advantages of high sensitivity and high selectivity for the detection of DOX in a simulated environment of human urine and serum.

Accompanied by condensation cyclization reactions in solvothermal conditions, three Gd(III) tetranuclear clusters {[ Gd-4(L-x)(2)( mu(3)-OH)(2)(NO3)(2)(Ac)(6)]} (x = 1, 2, and 3 for 1, 2, and 3, respectively) were isolated and characterized, wherein, L1-3 were in situ synthesized from bis[3-(pyridin-2-yl)-1H-1,2,4-triazole-5-yl]methane (bptm), 5-bptm (bis[3-(5-methylpyridin-2-yl)-1H-1,2,4-triazole-5-yl]methane), and 4-bptm (bis[3-(4-methylpyridin-2-yl)-1H-1,2,4-triazole-5-yl]methane) in the presence of Gd-III ions, respectively. The step-by-step formation process (bptm -> L-1 -> Gd-1(L-1)(1) -> Gd-2(L-1)(1) -> Gd-2(L-1)(2) -> Gd-3(L-1)(2) -> Gd-4(L-1)(2)) of the tetranuclear clusters in 1 was tracked by mass spectrometry technology. The study of their magnetic properties showed that 1-3 displayed significant magnetocaloric effects with the -Delta S-m values of 29.25-29.64 J K-1 kg(-1).