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Metal-organic polyhedra (MOPs) are a subclass of coordination cages that can adsorb and host species in solution and are permanently porous in solid-state. These characteristics, together with the recent development of their orthogonal surface chemistry and the assembly of more stable cages, have awakened the latent potential of MOPs to be used as building blocks for the synthesis of extended porous networks. This review article focuses on exploring the key developments that make the extension of MOPs possible, highlighting the most remarkable examples of MOP-based soft materials and crystalline extended frameworks. Finally, the article ventures to offer future perspectives on the exploitation of MOPs in fields that still remain ripe toward the use of such unorthodox molecular porous platforms.
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http://dx.doi.org/10.1002/advs.202104753 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1RX, UK.
Porous metal-organic polyhedra (MOPs) have strong covalent and coordinate bonds that define the intrinsic pore of the cage. The intermolecular interactions between cages tend to be weaker, such that they rearrange during the solvent exchange process preceding gas sorption measurements. The reduction in crystal size that this often causes limits the availability of structural data that could enable understanding of observed gas uptake.
View Article and Find Full Text PDFAdv Mater
July 2025
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Conquering the sluggish kinetics of the oxygen reduction reaction (ORR) is significantly important for sustainable metal-air batteries. However, the synthesis of advanced Pt-free ORR electrocatalysts still remains challenging owing to the intrinsic activity, site accessibility, and structural stability. Herein, a catalyst of asymmetric N, P-coordinated Mn and Fe dual single atoms supported on hollow carbon polyhedra (MnFe-PNC) is synthesized via a metal-organic framework pyrolysis strategy, which displays excellent pH-universal ORR performance with half-wave potentials of 0.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2025
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
To gain a better understanding of the processes with which metal-organic frameworks (MOFs) self-assemble, we construct a coarse-grained simulation toolkit to model the growth of a wide variety of MOF structure types. We employ the topology and symmetry of the underlying net of the framework structure to design building blocks that correspond to MOF components. Sphere-union polyhedra are constructed to model MOF nodes by choosing the types and positions of simulation beads, as well as the specific interactions between them, to correspond to the node coordination and local symmetry.
View Article and Find Full Text PDFMater Horiz
July 2025
State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University, 201620 Shanghai, P. R. China.
Metal-organic polyhedra (MOP)-based composites have emerged as promising candidates for various applications owing to their unique structure. However, the construction of strong and recyclable MOP-based composites with novel functionalities is challenging. Herein, by using telechelic aromatic polyamides as macromolecular ligands, crosslinked MOP polyamides (LODA-MOPs) were constructed coordination with copper ions (Cu).
View Article and Find Full Text PDFSmall
August 2025
School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China.
As an emerging class of porous solid materials, metal-organic polyhedra (MOPs), possess inherent porosity and excellent solvent processability, making them highly promising candidates for membrane separation applications. However, the development of continuous and structurally stable MOP-based membranes remains a significant challenge due to the weak noncovalent intermolecular interactions. Herein, an intermolecular transitions strategy is implemented to enhance the intermolecular interactions within MOPs molecules.
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