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Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr₆ clusters.

ABSTRACT: Zirconium-based metal-organic frameworks (Zr-MOFs) have been extensively studied due to their very rich structural chemistry. The combination of nearly unlimited carboxylic acid-based linkers and Zr₆ clusters with multiple connectivities has led to diverse structures and specific properties of resultant Zr-MOFs. Herein, we demonstrate the successful use of reticular chemistry to construct two novel Zr-MOFs, HIAM-4040 and HIAM-4040-OH, with zfu topology. Based on a thorough structural analysis of (4,4)-connected lvt-type Zr-tetracarboxylate frameworks and a judicious linker design, we have obtained the first example of a Zr-pentacarboxylate framework featuring unprecedented 5-connected organic linkers and 5-connected Zr₆ clusters. Compared with HIAM-4040, a larger Stokes shift is achieved in HIAM-4040-OH via hydroxyl group induced excited-state intramolecular proton transfer (ESIPT). HIAM-4040-OH exhibits high chemical and thermal stability and is used for HClO detection in aqueous solution with excellent sensitivity and selectivity.

SUBMITTER: Peng T

PROVIDER: S-EPMC10901486 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr<sub>6</sub> clusters.

Peng Tianyou T Han Chao-Qin CQ Xia Hai-Lun HL Zhou Kang K Zhang Jian J Si Jincheng J Wang Lei L Miao Jiafeng J Guo Fu-An FA Wang Hao H Qu Lu-Lu LL Xu Guozhong G Li Jing J Liu Xiao-Yuan XY

Chemical science 20240123 9

Zirconium-based metal-organic frameworks (Zr-MOFs) have been extensively studied due to their very rich structural chemistry. The combination of nearly unlimited carboxylic acid-based linkers and Zr<sub>6</sub> clusters with multiple connectivities has led to diverse structures and specific properties of resultant Zr-MOFs. Herein, we demonstrate the successful use of reticular chemistry to construct two novel Zr-MOFs, HIAM-4040 and HIAM-4040-OH, with zfu topology. Based on a thorough structural ...[more]

PMID: 38425507

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Project description: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 [Fe3(μ3-Ο)(-COO)6]+ clusters. The tbb's are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe3(μ3-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, CH4, and CO2 at 87, 112, and 195 K, respectively, revealing an ultrahigh BET area (4263-4847 m2 g-1) and pore volume (1.95-2.29 cm3 g-1). Because of the observed ultrahigh porosities, the H2 and CH4 storage properties of Fe-tbb-MOF-x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryoadsorptive H2 storage (11.6 wt %/41.4 g L-1, 77 K/100 bar-160 K/5 bar), as well as CH4 storage at near ambient temperatures (367 mg g-1/160 cm3 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.

Dataset Information

Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr₆ clusters.

Publications

Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr<sub>6</sub> clusters.

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Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr6 clusters.

Publications

Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr<sub>6</sub> clusters.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr₆ clusters.