Superexchange-like interaction of encaged molecular oxygen in nitrogen-doped water cages of clathrate hydrates

Download
  1. Get@NRC: Superexchange-like interaction of encaged molecular oxygen in nitrogen-doped water cages of clathrate hydrates (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/ja2081394
AuthorSearch for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume133
Issue50
Pages2039920404; # of pages: 6
SubjectAntiferromagnetics; Clathrate hydrate; Dioxygen molecules; Dioxygens; Environmental fields; Experimental approaches; Guest molecules; Host guest interactions; Hydrate cages; Inclusion compounds; Magnetic applications; Magnetic ions; Nitrogen-doped; Nonmagnetics; Novel materials; Orbitals; Spin couplings; Super-exchange coupling; Theoretical calculations; Water cage; Antiferromagnetism; Cobalt compounds; Hydration; Manganese oxide; Molecular oxygen; Hydrates; ammonia; clathrate hydrate; hydroxide; ion; manganese oxide; nitrogen; oxygen; unclassified drug; water; article; density functional theory; magnetism; oxidative coupling; spin coupling
AbstractClathrate hydrates are a highly prospective material in energy and environmental fields, but the inherent nature of inclusion phenomena occurring in the stacked water cages has not been completely resolved yet. Investigating the magnetism of guest molecules is a new experimental approach in clathrate hydrate research to open the possibility of icy magnetic applications as a novel material as well as to understand the unrevealed host-guest interactions in icy inclusion compounds. In this study, we observed an indirect spin coupling between encaged dioxygen molecules via a nonmagnetic water framework through the measurement of guest magnetization. This spin coupling is reminiscent of superexchange coupling between magnetic ions through intervening oxygens in antiferromagnetic oxides, such as MnO and CoO. Theoretical calculations revealed that OH - incorporated in the framework induced the mixing of perpendicular π* orbitals of two distant dioxygens and that ammonia doping into the hydrate cage leads to a longer lifetime of that orientation. © 2011 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21271758
Export citationExport as RIS
Report a correctionReport a correction
Record identifierebd215e2-c439-4d86-a0dd-e51c47e003f0
Record created2014-03-24
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)