title: Pyrrolo-annelated tetrathiafulvalenes: the parent systems
abstract: The synthesis of a number pyrrolo-annelated tetrathiafulvalenes, including the parent bis(pyrrolo[3,4-d])tetrathiafulvalene (7) is decribed. Starting from readily available 4,5-bis(bromomethyl)-1, 3-dithiole-2-thione (14) and sodium tosylamide, the parent 7 and the asymmetric monopyrrolo tetrathiafulvalenes 23a,b were prepared in good yields via a nonclassical and simple pyrrole synthesis. Furthermore, a series of asymmetrical N-alkylated monopyrrolo/monodihydropyrrolotetrathiafulvalenes was prepared starting from primary amines and 14. A detailed study of the fundamental redox behavior of this class of heterocycles is reported. NMR spectroscopy, cyclic voltammetry, and PM3 MO calculations revealed that the pyrrolo-annelated tetrathiafulvalenes have highly extended pi-surfaces. The X-ray crystallographic analyses of the monopyrrolo tetrathiafulvalenes 22b and 24b, together with preliminary formation of a charge-transfer complex between the parent donor 7 and TCNQ, are also reported.
authors.affiliation: Department of Chemistry, SDU, Odense University, Campusvej 55, DK-5230 Odense M, Denmark, and Department of Chemistry, The Technical University of Denmark, DK-2800 Lyngby, Denmark.
authors.initials: JO
authors.lastname: Jeppesen
authors.initials: K
authors.lastname: Takimiya
authors.initials: F
authors.lastname: Jensen
authors.initials: T
authors.lastname: Brimert
authors.initials: K
authors.lastname: Nielsen
authors.initials: N
authors.lastname: Thorup
authors.initials: J
authors.lastname: Becher