Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework

Peng Li; Subhadip Goswami; Ken Ichi Otake; Xingjie Wang; Zhijie Chen; Sylvia L. Hanna; Omar K. Farha

doi:10.1021/acs.inorgchem.8b03511

Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework

Peng Li, Subhadip Goswami, Ken Ichi Otake, Xingjie Wang, Zhijie Chen, Sylvia L. Hanna, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th ₆ (μ ₃ -O) ₂ (HCOO) ₄ (H ₂ O) ₆ (TCPP) ₄ ] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th ₆ (μ ₃ -O) ₂ (HCOO) ₄ (H ₂ O) ₆ ], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.

Original language	English (US)
Pages (from-to)	3586-3590
Number of pages	5
Journal	Inorganic chemistry
Volume	58
Issue number	6
DOIs	https://doi.org/10.1021/acs.inorgchem.8b03511
State	Published - Mar 18 2019

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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10.1021/acs.inorgchem.8b03511

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title = "Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework",

abstract = " The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 (TCPP) 4 ] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 ], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.",

author = "Peng Li and Subhadip Goswami and Otake, {Ken Ichi} and Xingjie Wang and Zhijie Chen and Hanna, {Sylvia L.} and Farha, {Omar K.}",

note = "Funding Information: The authors gratefully acknowledge funding from the Actinide Center of Excellence (U.S. Department of Energy, National Nuclear Security Administration, under Award DE-NA0003763). We also acknowledge the Integrated Molecular Structure Education and Research Center facilities at North-western University, where PXRD and SCXRD measurements were performed. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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AU - Li, Peng

AU - Goswami, Subhadip

AU - Otake, Ken Ichi

AU - Wang, Xingjie

AU - Chen, Zhijie

AU - Hanna, Sylvia L.

AU - Farha, Omar K.

N1 - Funding Information: The authors gratefully acknowledge funding from the Actinide Center of Excellence (U.S. Department of Energy, National Nuclear Security Administration, under Award DE-NA0003763). We also acknowledge the Integrated Molecular Structure Education and Research Center facilities at North-western University, where PXRD and SCXRD measurements were performed. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/3/18

Y1 - 2019/3/18

N2 - The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 (TCPP) 4 ] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 ], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.

AB - The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 (TCPP) 4 ] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 ], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.

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Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework

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CCDC 1873150: Experimental Crystal Structure Determination

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Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework

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CCDC 1873150: Experimental Crystal Structure Determination

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