Unusual Metal-Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry

Sara E. Gilson; Melissa Fairley; Sylvia L. Hanna; Jennifer E.S. Szymanowski; Patrick Julien; Zhijie Chen; Omar K. Farha; Jay A. Laverne; Peter C. Burns

doi:10.1021/jacs.1c08854

Unusual Metal-Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry

Sara E. Gilson, Melissa Fairley, Sylvia L. Hanna, Jennifer E.S. Szymanowski, Patrick Julien, Zhijie Chen, Omar K. Farha, Jay A. Laverne, Peter C. Burns

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

17 Scopus citations

Abstract

A Np(V) neptunyl metal-organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γrays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl-actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γrays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.

Original language	English
Pages (from-to)	17354-17359
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	143
Issue number	42
DOIs	https://doi.org/10.1021/jacs.1c08854
State	Published - Oct 27 2021
Externally published	Yes

Funding

The initial part of this work was supported by the National Nuclear Security Administration, U.S. Department of Energy (DOE), under Award DE-NA0003763. The later part of this work was supported by the University of Notre Dame. The Materials Characterization Facility of the Center for Sustainable Energy at Notre Dame provided diffraction instrumentation. The authors thank Professor Ian Carmichael for making available the facilities of the Notre Dame Radiation Laboratory, which is supported by DOE BES Grant DE-FC02-04ER15533. S.E.G. thanks Dr. Evgenii Kovrigin for his help with the NMR instrument, the Magnetic Resonance Facility at the University of Notre Dame for use of their instruments, and Dr. Allen Oliver for useful crystallographic conversations. This contribution is NDRL-5330 from the Notre Dame Radiation Laboratory. S.L.H. acknowledges support from the DOE National Nuclear Security Administration Stewardship Science Graduate Fellowship (DOE NNSA SSGF) under Award DE-NA0003960.

Funders	Funder number
DOE NNSA SSGF	DE-NA0003960
U.S. Department of Energy	DE-NA0003763
Basic Energy Sciences	DE-FC02-04ER15533
National Nuclear Security Administration
University of Notre Dame

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title = "Unusual Metal-Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry",

abstract = "A Np(V) neptunyl metal-organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γrays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl-actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γrays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.",

author = "Gilson, {Sara E.} and Melissa Fairley and Hanna, {Sylvia L.} and Szymanowski, {Jennifer E.S.} and Patrick Julien and Zhijie Chen and Farha, {Omar K.} and Laverne, {Jay A.} and Burns, {Peter C.}",

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AU - Julien, Patrick

AU - Chen, Zhijie

AU - Farha, Omar K.

AU - Laverne, Jay A.

AU - Burns, Peter C.

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N2 - A Np(V) neptunyl metal-organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γrays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl-actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γrays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.

AB - A Np(V) neptunyl metal-organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γrays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl-actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γrays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.

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Unusual Metal-Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry

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