Isoreticular Contraction of Metal–Organic Frameworks Induced by Cleavage of Covalent Bonds

Yang, Yunhui; Fernández-Seriñan, Pilar; Imaz, Inhar; Gándara, Felipe; Handke, Marcel; Ortín‐Rubio, Borja; Juanhuix, Jordi; Maspoch, Daniel

doi:10.1021/jacs.3c05469

Cited by 7 publications

(2 citation statements)

References 38 publications

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“…It is important to note that the combination of the linear 1,4-benzenedicarboxylate (bdc) and the triangular btb linkers in MIL-142A results in the formation of a superoctahedron and not a supertrigonal prism as observed in tbb (Figure S17). , …”

Section: Resultsmentioning

confidence: 99%

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra

Froudas,

Vassaki,

Papadopoulos

et al. 2024

J. Am. Chem. Soc.

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The chemistry of metal−organic frameworks (MOFs) continues to expand rapidly, providing materials with diverse structures and properties. The reticular chemistry approach, where well-defined structural building blocks are combined together to form crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these greatly reduce the number of possible structures. Toward this, building blocks with connectivity greater than 12 are highly desirable but extremely rare. We report here the discovery of novel 18-connected, trigonal prismatic, ternary building blocks (tbb's) and their assembly into unique MOFs, denoted as Fe-tbb-MOF-x (x: 1, 2, 3), with hierarchical micro-and mesoporosity. The remarkable tbb is an 18-c supertrigonal prism, with three points of extension at each corner, consisting of triangular (3-c) and rectangular (4-c) carboxylate-based organic linkers and trigonal prismatic [Fe 3 (μ 3 -Ο)(−COO) 6 ] + clusters. The tbb's are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe 3 (μ 3 -Ο) trimer, forming overall a 3-D (3,4,4,6,6)-c five nodal net. The hierarchical, highly porous nature of Fe-tbb-MOF-x (x: 1, 2, 3) was confirmed by recording detailed sorption isotherms of Ar, CH 4 , and CO 2 at 87, 112, and 195 K, respectively, revealing an ultrahigh BET area (4263−4847 m 2 g −1 ) and pore volume (1.95−2.29 cm 3 g −1 ). Because of the observed ultrahigh porosities, the H 2 and CH 4 storage properties of Fe-tbb-MOF-x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryoadsorptive H 2 storage (11.6 wt %/41.4 g L −1 , 77 K/100 bar−160 K/5 bar), as well as CH 4 storage at near ambient temperatures (367 mg g −1 /160 cm 3 STP cm −3 , 5−100 bar at 298 K), placing these materials among the top performing MOFs. The present work opens new directions to apply reticular chemistry for the construction of novel MOFs with tunable porosities based on contracted or expanded tbb analogues.

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Section: Resultsmentioning

confidence: 99%

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra

Froudas,

Vassaki,

Papadopoulos

et al. 2024

J. Am. Chem. Soc.

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“…[ 17 ] In addition to these bottlenecks, it remains a challenge to control size and spatial arrangement of the hierarchical pores, not only for the stability of the overall MOF framework, but likewise for maintaining the integrity of the mesoscale cavities. [ 18–20 ]…”

Section: Introductionmentioning

confidence: 99%

Hierarchically Micro‐ and Mesoporous Zeolitic Imidazolate Frameworks Through Selective Ligand Removal

Huang,

Rath,

Zhou

et al. 2023

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A new method to engineer hierarchically porous zeolitic imidazolate frameworks (ZIFs) through selective ligand removal (SeLiRe) is presented. This innovative approach involves crafting mixed‐ligand ZIFs (ML‐ZIFs) with varying proportions of 2‐aminobenzimidazole (NH2‐bIm) and 2‐methylimidazole (2‐mIm), followed by controlled thermal treatments. This process creates a dual‐pore system, incorporating both micropores and additional mesopores, suggesting selective cleavage of metal‐ligand coordination bonds. Achieving this delicate balance requires adjustment of heating conditions for each mixed‐ligand ratio, enabling the targeted removal of NH2‐bIm from a variety of ML‐ZIFs while preserving their inherent microporous framework. Furthermore, the distribution of the initial thermolabile ligand plays a pivotal role in determining the resulting mesopore architecture. The efficacy of this methodology is aptly demonstrated through the assessment of hierarchically porous ZIFs for their potential in adsorbing diverse organic dyes in aqueous environments. Particularly striking is the performance of the 10%NH2‐ZIF‐2 h, which showcases an astonishing 40‐fold increase in methylene blue adsorption capacity compared to ZIF‐8, attributed to larger pore volumes that accelerate the diffusion of dye molecules to adsorption sites. This versatile technique opens new avenues for designing micro/mesoporous ZIFs, particularly suited for liquid media scenarios necessitating efficient active site access and optimal diffusion kinetics, such as purification, catalysis, and sensing.

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Covalent-Metal organic Frameworks: Preparation and applications

Wang,

et al. 2024

Chemical Engineering Journal

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Isoreticular Contraction of Metal–Organic Frameworks Induced by Cleavage of Covalent Bonds

Cited by 7 publications

References 38 publications

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra

Hierarchically Micro‐ and Mesoporous Zeolitic Imidazolate Frameworks Through Selective Ligand Removal

Covalent-Metal organic Frameworks: Preparation and applications

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