Synthetic Control of Thorium Polyoxo-Clusters in Metal–Organic Frameworks toward New Thorium-Based Materials

Li, Peng; Wang, Xingjie; Otake, Ken-ichi; Lyu, Jiafei; Hanna, Sylvia L.; Islamoglu, Timur; Farha, Omar K.

doi:10.1021/acsanm.9b00188

Title: Synthetic Control of Thorium Polyoxo-Clusters in Metal–Organic Frameworks toward New Thorium-Based Materials

Journal Article · Fri Mar 15 00:00:00 EDT 2019 · ACS Applied Nano Materials

DOI:https://doi.org/10.1021/acsanm.9b00188· OSTI ID:1502932

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Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology; South China Univ. of Technology, Guangzhou (China)
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology; Tianjin Univ., Tianjin (China). Dept. of Pharmaceutical Engineering, School of Chemical Engineering and Technology

Control over the assembly of thorium-based polyoxo-clusters remains a great challenge because of their quick olation and oxolation reactions. Here, we report the synthesis and isolation of two pure phase thorium polyoxocluster-based metal-organic frameworks (Th-MOFs), ThNU-1008 and Th-NU-1011. Crystal structures of these ThMOFs reveal two distinct 8-connected polyoxo-clusters: a hexanuclear cluster [Th₆(μ₃-O)₄(OH)₄(H₂O)₆(HCOO)₄] was observed in Th-NU-1008 and a tetranuclear cluster [Th₄(μ₃-)₂(OH)₄(DMF)₂(H₂O)₄] in Th-NU-1011 which has never been reported before among thorium species. In both Th-NU-1008 and Th-NU-1011, the tetratopic linker, 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl) benzene, joins the clusters together, forming two three-periodic networks, each with csq topology. The Brunauer-Emmett-Teller (BET) surface areas calculated from the Ar isotherms are approximately 800 and 700 m² g^-1 for Th-NU-1008 and Th-NU-1011, respectively. Because the linkers are oriented orthogonal to each other in the two respective MOFs, a 32 Å hexagonal channel is observed in Th-NU-1008 while a 15 Å channel is observed in Th-NU-1011. This work opens a new avenue to construct unexplored Th-MOF materials with targeted polyoxo-cluster structures.

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Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003763

OSTI ID:: 1502932

Journal Information:: ACS Applied Nano Materials, Vol. 2, Issue 4; ISSN 2574-0970

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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Title: Synthetic Control of Thorium Polyoxo-Clusters in Metal–Organic Frameworks toward New Thorium-Based Materials

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