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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 733906.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Dinitreno pentaradicals: organic sextet molecules
Authors:Mieres-Perez, Joel; Henkel, Stefan; Mendez-Vega, Enrique; Schleif, Tim; Lohmiller, Thomas; Savitsky, Anton; Sander, Wolfram
Date of Publication (YYYY-MM-DD):2017
Title of Journal:Journal of Physical Organic Chemistry
Journal Abbrev.:J.Phys.Org.Chem.
Issue / Number:4 Sp. Iss. SI
Start Page:e3621
End Page:e3621
Sequence Number of Article:e3621
Review Status:Internal review
Audience:Experts Only
Abstract / Description:A new sextet ground state molecule, the 2,4,6-trichloro-1,3-dinitrenophenoxyl radical, was obtained upon UV photolysis of the corresponding diazido precursor in argon at 5 K. The sextet molecule is formed stepwise with the triplet nitrene, the quartet nitreno radical, and the quintet dinitrene as intermediates that were detected by EPR spectroscopy. IR and UV-Vis measurements only allowed us to observe the main product, the quintet dinitrene. The coupling between the two nitrene centers and the oxygen centered radical in the sextet state results in zero-field splitting (zfs) parameters of | D/hc| = 0.088 cm(-1) and | E/hc| = 0.009cm(-1), considerably larger than in previously reported organic sextet molecules. An analogous sextet dinitrene formed by replacing the oxygen centered radical by a carbon centered radical was also studied by EPR spectroscopy, and in this case the zfs parameters | D/hc| = 0.125 cm(-1) and | E/hc| = 0.023cm(-1) indicate even larger spin localization. Copyright (C) 2016 John Wiley & Sons, Ltd.
Comment of the Author/Creator:Date: 2017, APR 2017
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000398090200007 [ID No:1]
ISSN:0894-3230 [ID No:2]
DOI:10.1002/poc.3621 [ID No:3]
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