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Visualization of Iodine Chemisorption Facilitated by Aryl C-H Bond Activation

Title
Visualization of Iodine Chemisorption Facilitated by Aryl C-H Bond Activation
Authors
Lee, ByeongchanChen, Ying-PinPark, JinkyuPark, Jinhee
DGIST Authors
Park, Jinhee
Issue Date
2019-06
Citation
ACS Applied Materials and Interfaces, 11(29), 25817-25823
Type
Article
Article Type
Article
Author Keywords
iodine capturechemisorptionmetal-organic frameworksaryl C-H bond activationsingle crystal-single crystal transformation
Keywords
METAL-ORGANIC FRAMEWORKSRADIOACTIVE IODINESINGLE-CRYSTALGUEST BINDINGM-2(DOBDC) MCAPTUREADSORPTIONGASFENI
ISSN
1944-8244
Abstract
The ability to chemisorb iodine is important for the safe long-term storage of fission products from nuclear reactors. Herein, we successfully used single-crystal X-ray diffraction analysis to crystallographically visualize I2 binding sites in two isostructural metal-organic frameworks, viz. Co2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) and Co2(p-DOBDC) (p-DOBDC4- = 2,5-dioxo-1,4-benzenedicarboxylate), with increasing I2 loading. Interestingly, the C-H bond at the electron-rich carbon (C5) of m-DOBDC4- is activated toward electrophilic aromatic substitution, forming an aryl C-I bond and I- or I3 - that coordinates to unsaturated open Co sites. Cooperation between the ligand and the open Co sites leads to rapid chemisorption of I2 even under mild adsorption conditions, such as room temperature. In contrast, molecular I2 coordinates to the open Co sites of Co2(p-DOBDC). Owing to the chemisorption of I2, I2@Co2(m-DOBDC) decomposes at a much higher temperature than I2@Co2(p-DOBDC), as revealed by thermogravimetric analysis. © 2019 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/10405
DOI
10.1021/acsami.9b04768
Publisher
American Chemical Society
Related Researcher
  • Author Park, Jinhee Organic-Inorganic Hybrids Lab
  • Research Interests Organic-Inorganic Hybrid Materials; Metal-Organic Polyheda;Metal-Organic Frameworks; Porous Polymer Networks
Files:
There are no files associated with this item.
Collection:
Department of Emerging Materials ScienceOrganic-Inorganic Hybrids Lab1. Journal Articles


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