Klaus B. Simonsen

Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes bearing CN(CH2)2X and HO(CH2)2X groups (X = S or Se)

Several unsymmetrically substituted TTFs bearing the S(CH2)2CN protecting group have been prepared by standard cross coupling in triethyl phosphite from the key intermediate 4,5-bis(2′-cyanoethylsulfanyl)1,3-dithiol-2-one 1 and an appropriate 1,3-dichalcogenole-2-chalcogenone, 2–8. TTFs 10, 11 and 12 of type I have been obtained in satisfactory yields (30–60%) and those (13,14) of type II in low yields (10 and 19%) as a result of differences in the reactivity of the species involved.Pseudo-Wittig condensations from the key triphenylphosphonium salt 15 have allowed considerable improvement in the synthesis of 13 (70% yield) and 14 (57% yield).The diselena analogue of 1, 21 has also been obtained. Its derivative 22, a new tetrakis(alkylselena) functionalised TTF, has been isolated in fair yield (69%). Its deprotection in a basic medium followed by a subsequent alkylation has led to BEDSe-TTF 23 (40%). Finally, the same sequence of deprotectionrealkylation carried out from unsymmetric species 10 and 12 has successfully been used in a high yield preparation of the corresponding new functionalised TTFs bearing two hydroxyethyl groups.

Synthesis and X-ray crystal structure of the first tetrathiafulvalene-based acceptor–donor–acceptor sandwich

The synthesis and characterization of the bis-macrocyclic A–D–A sandwich 4·4PF6 produced in a simple one-pot reaction is reported; only one acceptor unit participates in charge-transfer interactions with the TTF unit in the solid state of 4·4PF6.

Tetrathiafulvalenes in Macrocyclic and Supramolecular Chemistry: Self Assembly with Tetrathiafulvalenes

We describe that use of stepvise selective protectiondeprotection of tetrathiafulvalene (TTF)-thiolates give rise to either two or three-dimensional macrobicyclic tetrathiafulvalenophanes in high yields by convergent syntheses. Configurationally selective selfassembly of cyclic tetrathiafulvalenes using the cyclic π-acceptor cyclo-bis(paraquat-p-phenylene) yields [2]- or [3]pseudocatenanes. A simple method for the preparation of donor-acceptor tetrathiafulvalenophanes is reported.