The rational design of metal-organic frameworks (MOFs) is one of the driving forces behind the great success that this class of materials is experiencing. The so-called isoreticular approach is a key design tool, very often used to tune the size, steric properties, and additional functional groups of the linker used. In this work, we go one step further and show that even linkers with two different coordinating groups, namely, phosphonate and phosphinate, can form isoreticular MOFs. This effectively bridges the gap between MOFs utilizing phosphinate and phosphonate coordinating groups. Using a novel bifunctional ligand, 4-[hydroxy(methyl)phosphoryl]phenylphosphonic acid [HPPP(Me)], we were able to prepare ICR-12, a MOF isoreticular to already published MOFs containing bisphosphinate linkers (e.g., ICR-4). An isostructural MOF ICR-13 was also successfully prepared using 1,4-benzenediphosphonic acid. We envisage that this strategy can be used to further enlarge the pool of MOFs.
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http://dx.doi.org/10.1021/acs.inorgchem.2c03271 | DOI Listing |
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January 2025
Departamento de Física de la Materia Condensada, Universidad Autónoma de Madrid, Madrid, 28049, Spain.
Conductive metal-organic frameworks (MOFs) are crystalline, intrinsically porous materials that combine remarkable electrical conductivity with exceptional structural and chemical versatility. This rare combination makes these materials highly suitable for a wide range of energy-related applications. However, the electrical conductivity in MOF-based devices is often limited by the presence of different types of structural disorder.
View Article and Find Full Text PDFAdv Mater
January 2025
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China.
The design and synthesis of metal-organic frameworks (MOFs) with outstanding light-harvesting and photoexcitation for artificial photocatalytic CO reduction is an attractive but challenging task. In this work, a novel aggregation-induced emission (AIE)-active ligand, tetraphenylpyrazine (PTTBPC) is proposed and utilized for the first time to construct a Zr-MOF photocatalyst via coordination with stable Zr-oxo clusters. Zr-MOF is featured by a scu topology with a two-fold interpenetrated framework, wherein the PTTBPC ligands enable strong light-harvesting and photoexcitation, while the Zr-oxo clusters facilitate CO adsorption and activation, as well as offer potential sites for further metal modification.
View Article and Find Full Text PDFDalton Trans
January 2025
Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060, Nishikawatsu, Matsue, Shimane, 690-8504, Japan.
Paddlewheel-type diruthenium(II,II) complexes are paramagnetic with two unpaired electrons ( = 1) and can be utilized as versatile building blocks for higher-order structures, such as supramolecular complexes, coordination polymers, and metal-organic frameworks, although they are generally highly air-sensitive. In this study, we developed an air-stable paddlewheel-type diruthenium(II,II) complex with two electron-withdrawing 1,8-naphthyridine-2-carboxylate (npc) ligands, [Ru(μ-npc)(OCMe)] (1). The two acetate ligands in 1 can be replaced by other carboxylate ligands; the solvothermal reactions of 1 with benzoic acid (HOCPh) yields the heteroleptic [Ru(μ-npc)(OCPh)] (2), whereas its reaction with 1,8-naphthyridine-2-carboxylic acid (Hnpc) produces the homoleptic [Ru(μ-npc)(η-npc)] (3).
View Article and Find Full Text PDFChemSusChem
January 2025
Leiden University: Universiteit Leiden, Leiden Institute of Chemistry, Einsteinweg 55, Room number EE4.19, 2333 CC, Leiden, NETHERLANDS, KINGDOM OF THE.
Electrocatalysis in metal-organic frameworks is an interplay between the diffusion of charges, the intrinsic catalytic rate, and the mass-transport of reactants through the pores. Here a systematic study is carried out to investigate the role of the electrolyte nature and concentration on the oxygen reduction reaction (ORR) with the PCN-224(Co) MOF in aqueous electrolyte. It was found that the ORR activity is slightly influenced by the nature of the ions in solution, providing that the ionic strength is high enough to minimize the resistivity during the measurement.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Department of Battery and Chemical Engineering, Hanyang University, Ansan, Gyeonggi-do 15588, Republic of Korea.
Designing and constructing hierarchically structured materials with heterogeneous compositions is the key to developing an effective catalyst for overall water-splitting applications. Herein, we report the fabrication of hollow-structured selenium-doped nickel-cobalt hybrids on carbon paper as a self-supported electrode (denoted as Se-Ni|Co/CP, where Ni|Co hybrids consist of nickel-cobalt alloy-incorporated nickel-cobalt oxide). The procedure involves direct growth of zeolitic imidazolate framework-67 (ZIF-67) on bimetal-based nickel-cobalt hydroxide (NiCoOH) electrodeposited on CP, followed by selenous etching and pyrolysis to obtain the final Se-Ni|Co/CP electrocatalytic system.
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