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Photochemistry without protons. Radical cation chemistry in zeolites [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy, 1994.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description
4 pages : digital, PDF file
Additional Creators
Argonne National Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The interconversion of the C₇H₈ molecular framework, especially norbornadiene (NBD) and quadricyclane (Q), has been considered for photochemical energy storage. Actually, very little was known about the details of these carbon-skeleton transformations, and only one radical cation species (NBD⁺·) was characterized. The authors have undertaken a thorough study of these systems using zeolite matrices. They have shown that zeolites have exceptional properties, allowing unprecedented control of chemical reactivity. In the attached scheme, they outline some of the species they were able to characterize. The crucial aspect of the zeolite matrix is that one can tune the matrix-radical cation interaction by varying the matrix polarity. The ZSM-5 zeolites of identical structure with different Si/Al ratio are ideally suited for such study. Without discussing all the transformations, the authors point that several processes, such as the reverse Diels-Alder reaction are known to occur by involvement of highly excited states. Such reactions in zeolites means that sites in the zeolite matrix are able to stabilize high electronic states of ions, significantly lowering the potential energy barrier for such reactions. Thus, they are able to thermally drive otherwise photodriven reactions.
Report Numbers
E 1.99:anl/chm/pp--77910
anl/chm/pp--77910
Subject(s)
Other Subject(s)
Note
Published through SciTech Connect.
06/01/1994.
"anl/chm/pp--77910"
"DE94012631"
Trifunac, A.D.; Barnabas, M.V.
Type of Report and Period Covered Note
Topical; 06/01/1994 - 06/01/1994
Funding Information
W-31109-ENG-38
View MARC record | catkey: 14100876