ABSTRACT The advancement of atomic‐level sulfurization technology is ushering materials engineering from coarse regulation toward precise editing. As represented by polyoxothiometalates (POTMs), the available sulfurization methods remain limited and nongreen, imposing severe constraints on their structural diversity and functional applications. In this study, an in situ sulfurization approach was developed to construct the Mo‐based POTMs (POTMos) in a distinct and eco‐friendly manner. The emergence of unprecedented building blocks gave birth to two POTMos featuring single or fused Mayan‐pyramidal frameworks. Enabled by the structural modulation and enhanced biocompatibility via sulfur incorporation, the Mo‐57‐oxothio polyanion ( Mo 57 ) demonstrated potent antitumor efficacy. Combined experimental and theoretical analyses revealed that Mo 57 could disrupt the cell respiratory chain via two synergistic routes: catalytic oxidation of NADH and electrostatic adsorption of NAD + . Such dual interference triggered mitochondrial dysfunction and a consequent inhibition of tumor proliferation.

Albeit the development of polyoxometalate (POM)-based antibiotics has spanned more than three decades, the antibacterial potential of Mo-based POMs (POMos) remains largely untapped. Given the prominent structure-dependent bioactivity of POMs, this study focuses on the structural engineering of wheel-shaped POMos in an attempt to boost their antibacterial performance. Adopting a dimethylarsinate-involved synthetic strategy, unprecedented iso- and hetero-POMo wheels constructed by emerging building blocks and assembly routes have been obtained. Of these, the [MoV12MoVI18O96]24- (Mo30) wheel demonstrated a 10-fold greater efficacy against methicillin-resistant Staphylococcus aureus (MRSA) than the conventional Keggin-type [PMo12O40]3- (PMo12), with the reduction of MIC from 1000 μg/mL (532.9 μmol/L, PMo12) to 100 μg/mL (17.7 μmol/L, Mo30). The significant decrease in biofilm mass from 93% (Mo30) to 16% (PMo12) signifies that the larger size and higher electronegativity of Mo30 might intensify the interaction with cell membrane proteins, resulting in membrane disruption and subsequent bacterial death. The established structure-bioactivity relationship for POMo wheels promises to revitalize research efforts toward POM-based antibiotics of the next generation.

Achieving predictable assembly of metal-organic polyhedra (MOPs) with targeted architectures from designed building blocks is a persistent fundamental challenge. Ligand engineering constitutes a pathway toward addressing this challenge. This work...

Precise control over metal-organic polyhedra (MOPs) architectures via metal and organic linker engineering presents a critical challenge for advancing functional porous materials with specific properties. The rational design of organic linkers and secondary building units (SBUs) with programmable configurational features facilitates the assembly of novel MOPs, wherein structural complexity is enhanced through the integration of low-symmetry linkers and expandable SBUs. Herein, a series of polyoxovanadate-based metal-organic polyhedra (VMOPs) with modulated structures were systematically engineered through linker desymmetrization and SBU expansion approach. Two types of tritopic triazine (D3h)- or imidazole (Cs/C1)-functionalized carboxylate ligands assemble with 3-connected prototype {V6S} or expansional {V6P} clusters, yielding VMOPs that exhibit structural evolution from Td-symmetric regular tetrahedrons to D2d-symmetric isosceles variants. Expansion of vertex clusters leads to structural fine-tuning of VMOPs, giving rise to diverse ligand conformations. Interestingly, these VMOPs exhibit significant differences during the iodine adsorption in both n-hexane solution and gaseous phases, which can be explained by the comprehensive influence of their cavity volume, the functional groups included, and the stacking arrangement. These findings demonstrate an effective structure-designing strategy via regulation of ligand symmetry and SBU architectural features, providing a powerful approach for the customized synthesis of MOPs with tailored structures and functionalities.

The upsurge of precision chemistry has put forward higher demands for material synthesis, along with the shift of research focus from structural assembly to the spatial arrangement of molecules in a desired manner. Herein, polyoxovanadates (POV) have been hired for regulating the distribution status of cucurbit[6]urils (CB[6]) in their coconstructed supramolecular frameworks. The outer-surface bindings between POV and CB[6] via noncovalent forces contribute greatly to improving the accessibility of macrocycles and stability of entire architectures. In this context, pyridine (py) and ethylenediamine (en) have been allowed to enter the pocket of CB[6], resulting in the respective host-guest complexes. Upon that, the distinct iodine adsorption performances of the as-made frameworks have been observed and analyzed. Supported by both experimental and theoretical data, it has been revealed that the smooth electron delivery from en to CB[6] could promote the ionization of I2 -> I3 -, thereby enhancing the adsorption efficiency significantly. By contrast, the encapsulated py prefers to weaken the electron supply of CB[6], thus blocking the reduction of iodine and quenching the adsorptive ability. As a result, the capture of iodine by such adsorbents can be switched on or off by altering the electron transfer routes within the host-guest systems.

Following the construction schemes of pyrgoscages and catenanes, attempts to splice polyoxovanadate‐based metal–organic polyhedra (POV‐MOPs) together have been carried out in this work. To meet the requirements of POV‐MOPs with varied sizes, synthetic strategies including reconstruction of original vertex, introduction of exogenous vertex, and initiative of polyhedral interlock have been developed, which successfully integrated a pair of tetrahedral monomers into an hourglass‐shaped dimer. On top of this, several structuring principles, such as anisotropic enhancement, electrostatic potential reduction, and sufficient intramolecular support, can be drawn from here and popularized to the related MOP systems. Thanks to the advent of such splicing techniques managed by both covalent and non‐covalent interactions, the close communication of POV‐MOPs has afforded not only the unprecedented structural archetypes, but the unique behaviors for NH 3 adsorption as well.

Photocatalytic fabrication of fine chemicals provides a sustainable method of development for the pharmaceutical industry. At present, optimizing the performance of photocatalysts via precise structural engineering at the atomic level is of the utmost importance. To unleash the potential of structurally editable polyoxovanadate-organic cages (POV-MOCs) as photocatalytic materials, herein, a family of five POV-MOCs were scaffolded by a cross combination of {V6X} (X = SO4 2-, PhPO3 2-, and NH2PhAsO3 2-) vertices and benzo-2,1,3-thiadiazole-functionalized carboxylate linkers. Along with the structural evolution from capsule to cuboid-type topology as well as the heterogroup modification of the vertex, the photophysical properties of POV-MOCs could be regulated precisely. The structurally optimized POV-MOCs demonstrated prominent photocatalytic activity in the oxidative synthesis of benzimidazoles, which are medicinally important. Thanks to the teamwork of experimental and theoretical studies, a possible reaction mechanism that involves O2 center dot- has been proposed and validated. The unveiled structure-function relationship provides an effective route to customize POV-MOC-based photocatalysts for a broader range of sustainable applications.

Bimetallic nanomaterials in conjunction with porous materials have emerged as the most promising catalytic materials for plasma‐assisted ammonia synthesis. Adopting appropriate synthesis strategies to regulate the morphology of porous materials and the bimetallic active components is a potential way to further enhance their catalytic performance. However, the role of the morphology and composition of the materials remains unclear. In this study, we synthesize composite catalysts (MnPd 12 /SBA15, CoPd 12 /SBA15, CuPd 12 /SBA15, and NiPd 12 /SBA15) by regulating the morphology of the support mesoporous silica (SBA15) and using polyoxopalladates, which can precisely control molecular structure, as a precursor for bimetallic nanomaterials. Then, the performances of these catalysts for plasma‐assisted ammonia synthesis are investigated. The results show that the NiPd 12 /SBA15 composite catalyst has the highest ammonia synthesis yield, with a sample of 85 mg achieving an ammonia concentration up to 9070 ppm, and the energy consumption is as low as 77.75 MJ/mol. Additionally, it demonstrates good stability in cyclic experiments. The synergistic effect of SBA15 and NiPd 12 enables the NiPd 12 /SBA15 catalyst to significantly enhance the yield of ammonia synthesis. It is due to the ability of NiPd 12 metals to stabilize the dissociation state of N 2 , while having a relatively weak affinity for NH x intermediates. This facilitates the desorption of NH 3 from the catalyst surface.

Inspired by the construction scheme of biomacromolecules, a hierarchical assembly based on the lacunary polyoxopalladate (POP) of [SrPd 12 O 6 (OH) 3 (PhAsO 3 ) 6 (OAc) 3 ] 4− (SrPd 12 ) has been achieved. As a structurally programmable molecular building block, SrPd 12 is used to evolve from monomer via dimer to supramolecular aggregates in a controlled manner. In such process, the open-shell-type monomers are covalently integrated into bowl- or cage-like dimers via a direct or indirect splicing strategy. Upon that, hydrogen bond and hydrophobic effects are further hired to fabricate supramolecular aggregates of varied host–guest archetypes, thereby completing a hierarchical construction. In consideration of the combined advantages of noble metals and polyoxometalates in cancer treatment, both in vitro and in vivo anti-tumor assays of these SrPd 12 -derived POPs were studied in detail. A structure-dependent anti-tumor activitywas observed, originating from an imbalance of damage and repair of DNA as anti-tumor mechanism.

The century-old inverted Keggin ion has been revisited in an effort to unleash its potential in the structural engineering and functional development of polyoxomolybdates (POMos). Over the past hundred years, attempts to program the metal-oxo scaffold of inverted Keggins have been conducted continually but without any success. In this work, a structurally inert, inverted Keggin-type POMo could finally be altered by means of a binary heterogroup-templated approach, resulting in the successful isolation of two lacunary species. The local structure and charge distribution of these species are adjustable, and hence they serve as available building blocks for the subsequent controlled assembly of a CeIII-incorporated derivative. From the plenary to the lacunary, the enclosed structure of the inverted Keggin has been opened up significantly, resulting in less steric hindrance, along with a transition from an electron neutral species to a negatively charged species. Owing to these beneficial properties, the emerging defect-containing polyanions demonstrated outstanding Lewis acid-base catalytic activity in the high efficiency production of pyrazoles.

Self-assembly is a natural way for primitive things to grow on earth. For long, mankind has been attracted by the mechanism of such assembly processes, in an attempt to manipulate the outcome by whatever chemical forces available. The study on molecular building blocks, with an emphasis on lacunary polyoxometalates (l-POMs), delivers a unique perspective on the formation of natural and synthetic phases (e.g., minerals and nanomachines). The tunability of structure, composition, and physicochemical property confers a competitive edge on l-POMs in the design and fabrication of materials with desired functions. In this contribution, we provide a structural overview of l-POMs that covers not only the classical members of polyoxotungstates, -molybdates, -vanadates, -niobates, and -tantalates, but also the recently emerged non-classical counterparts of polyoxotitanates, -ferrates, and -palladates also. The evolution paths of l-POMs in the course of isomerization, transformation, and fusion are summarized and proposed. The empirical rules that supervise structural switches are discussed as well, in an effort to mature the design of POM-based materials in a controlled manner.

Promoting the advancement of the structure and function of metastable substances is challenging but worthwhile. In particular, how to harness the entangled state and evolution path of labile porous structures has been at the forefront of research in molecular self-assembly. In this work, the metastable structures of polyoxovanadate-based metal-organic polyhedra (VMOPs) can be manually regulated, including separation of the interlocked aggregate by a ligand-widening approach as well as transformation from a tetrahedral to capsule-like scaffold via a vertice-remodeling strategy. In these processes, intra- and intermolecular π···π and C-H···π interactions have been recognized as the primary driving forces. Besides being responsible for commanding the structural evolvement of VMOPs, such weak interactions were able to program their spatial arrangements and hence the adsorption performances for dye and iodine. The successful use of such a weak force-dominated design concept beacons a feasible route for customization of the function-oriented metastable structures. Separation and transformation of the interlocked metastable VMOPs have been achieved via the respective ligand-widening approach and vertice-remodeling strategy. Not only their structures but also adsorption features could be well regulated by such a weak force-dominated design concept.

It is tough, but worth it, to break the simple and inflexible structure of high symmetry and low energy, such as the cuboid topology of polyoxopalladates (POPs). In this work, the heterometal-templated scaffold of arsenopalladates has afforded three nanocubes of [MIVPd12O8(AsO4)8]12- (M = SnIV, CeIV, and PbIV) and the long-sought nanostar of [PbIVPd15O10(AsO4)10]16-. The appropriate charge and radius of PbIV satisfied the uncommon host-guest assembly of both cubic and star archetypes simultaneously. More than that is the successful preparation of the methylphosphonate-capped [Pd15O10(MePO3)10]10- POP for the first time. According to the adjustable heterometals and heterogroups, the as-made POPs represent ideal subjects to reveal structure-dependent antitumor activity. It turns out that ROS-induced apoptosis mediated by arsenate functions is mainly responsible for the significant inhibition against cancers of different types, which heralds the design philosophy of POP-based antitumor metallodrugs of the next generation. Access to the long-sought nanostar of arsenopalladate is workable via host-guest assembly. The arsenate functions of such POP metallodrugs drive the ROS-induced apoptosis with great antitumor potential.

An adjustable template effect was employed to activate the evolution of polyoxovanadate-based metal–organic clusters, resulting in unprecedented structural archetypes as well as customized dye and iodine adsorption features.

Novel structures of polyoxometalates can be obtained by confining the synthons within specific nanospaces. This capability is what the confined synthetic method excels at. Within the cavity of {P8W48}, a novel multicomponent cluster comprising cationic FeIII and CeIII heterometals and PO43u2212 oxyanions was successfully nucleated for the first time. Alongside examining the structure and composition of this hostu2013guest assembly, thorough investigations were conducted into the enhanced peroxidase-like activity induced by the Fenton-active metallic species. Preliminary studies on a colorimetric sensor based on [{FeIII8CeIII4O2(OH)12(H2O)8(PO4)2}(P8W48O184)]26u2212 yielded promising results, demonstrating its ability to detect ascorbic acid with high sensitivity and specificity.

Novel structures of polyoxometalates might be obtained once the freedom of synthons is restricted in a specific nanospace.This is exactly what the confined synthetic method can do and skilled in.Within the cavity of {P8W48}, herein, the nucleation of an unprecedented, multi-component cluster of {Fe III 8Ce III 4O2(OH)12(H2O)8(PO4)2} that made up of both the cationic Fe III and Ce III heterometals as well as the PO4 3-oxyanions was succeeded for the first time.Aside from the focus on the structure and composition of such host-guest assembly, the enhanced peroxidase-like activity brought by the Fenton-active metallic species was investigated systematically.Preliminary studies on the availability of the [{Fe III 8Ce III 4O2(OH)12(H2O)8(PO4)2}(P8W48O184)]26--based colorimetric sensor received satisfactory results, showcasing the detection for ascorbic acid of high sensitivity and selectivity.