title: Bis-thioether-substituted perylene diimides: structural, electrochemical, and spectroelectrochemical properties.
abstract: The synthesis and separation of the 1,6- and 1,7- isomers of N,N'-bis(alkyl)diadamantylthio-3,4,9,10-perylenetetracarboxylic acid diimide are reported. Investigations of the structural, electrochemical, spectroscopic, and spectroelectrochemical properties of the isomers reveal a sequence of electrochemically and chemically reversible reduction processes for both isomers. Three X-ray crystal structures are reported including a pair of 1,6- and 1,7-isomers demonstrating the twist of the perylene core in the solid state. Our studies thoroughly characterize the mono- and direduced states of the two isomers allowing unequivocal characterization of the reduced species by UV-vis and IR spectroscopic measurements. EPR studies also allow direct identification of the monoreduced PTCDI species and spectroscopic measurements confirm the delocalization of electronic density around the carbonyl moieties of the reduced species.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Anna G
authors.initials: AG
authors.lastname: Slater
authors.forename: E Stephen
authors.initials: ES
authors.lastname: Davies
authors.forename: Stephen P
authors.initials: SP
authors.lastname: Argent
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.forename: Neil R
authors.initials: NR
authors.lastname: Champness
mesh_terms: D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D004578:Electron Spin Resonance Spectroscopy; D007094:Imides / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013440:Sulfides / Q000737:chemistry*
chemical_list: D007094:Imides; D013440:Sulfides; C521332:perylenediimide; D010569:Perylene