Synthesis and electrochemistry of 1,2,4,6-thiatriazine radicals
Roemmele, Tracey L.
University of Lethbridge. Faculty of Arts and Science
Lethbridge, Alta. : University of Lethbridge, Faculty of Arts and Science
1,2,4,6-thiatriazine radicals can be neutral radical conductors in the context of molecular metal design. After initial investigations they were ignored in favor of other prospective ring systems. A more general route to 1,2,6-thiatriazine radicals herein is reported. Two crystal structures were obtained for the radicals 5-phenyl-3-trichloromethyl-1,2,4,6-thiatriazine 7c and 5-phenyl-3-trifluoromethyl-1,2,4,6-thiatriazine 8c. 7c displays a unique head-to-tail packing arrangement not seen in previous thiatriazine structures. Two crystal structures of the precursor phenyl/trichloro imidoylamidine 1c and phenyl/trifluoromethyl imidoylamidine 2c show strong intramolecular hydrogen bonding and relatively weak intermolecular hydrogen bonding. EPR of the radicals are highly diagnostic and display coupling to three unique nitrogen atoms, of which a small but very distinct influence on the hyperfine coupling constants from the remote aryl-substituents is seen. Solution electrochemistry assessed the redox tunability of the radicals to these substituents. DFT calculations of the hyperfine coupling constants and oxidation and reduction potentials corroborated well with experimental data.
xv, 176 leaves : ill. ; 28 cm.
Organic conductors , Dissertations, Academic