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

Journal Article · · ACS Applied Nano Materials
 [1];  [2];  [3];  [4];  [3];  [3];  [3]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology; University of Notre Dame
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology; South China Univ. of Technology, Guangzhou (China)
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and International Inst. of Nanotechnology
  4. 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
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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.
Research Organization:
Univ. 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, Journal Name: ACS Applied Nano Materials Journal Issue: 4 Vol. 2; ISSN 2574-0970
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Mononuclear to Polynuclear U IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation journal April 2020
Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands journal January 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY
crystal transformation
csq topology
hexamer
metal−organic framework
tetramer
thorium cluster