Synthesis and electrochemistry of 1,2,4,6-thiatriazine radicals

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.

Grantor dc:publisher

Lethbridge, Alta. : University of Lethbridge, Faculty of Arts and Science

Year dc:date.issued

2002

Authors dc:creator

• Roemmele, Tracey L.
• University of Lethbridge. Faculty of Arts and Science

Advisor dc:contributor.supervisor

• Boeré, René T.

• Organic conductors
• Dissertations, Academic

Language dc:language.iso

en_US

Identifier

hdl:10133/197

OAI record oai:identifier

https://opus.uleth.ca/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Aopus.uleth.ca%3A10133%2F197