DOUBLE-BOND SHIFTS IN [4N]ANNULENES AS A NEW PRINCIPLE FOR MOLECULAR SWITCHES - FIRST RESULTS WITH DIMETHYL HEPTALENE-1,2-DICARBOXYLATES AND HEPTALENE-4,5-DICARBOXYLATES

A new concept for molecular switches, based on thermal or photochemica l double-bond shifts (DBS) in [4n]annulenes such as heptalenes or cycl ooctatetraenes, is introduced (cf: Scheme 2). Several heptalene-1,2- a nd -4,5-dicarboxylates (cf: Scheme 4) with (E)-styryl and Ph groups at C(5) and C(1), or C(4) and C(2), respectively, have been investigated . Several X-ray crystal-structure analyses (cf. Figs. 1-5) showed that the (E)-styryl group occupies in the crystals an almost perfect s-tra ns-conformation with respect to the C=C bond of the (E)-styryl moiety and the adjacent C=C bond of the heptalene core. Supplementary H-1-NOE measurements showed that the s-trans-conformations are also adopted i n solution (cf. Schemes 6 and 9). Therefore, the DBS process in heptal enes (cf: Schemes 5 and 8) is always accompanied by a 1800 torsion of the (E)-styryl group with respect to its adjacent C=C bond of the hept alene core. The UV/VIS spectra of the heptalene-1,2- and -4,5-dicarbox ylates illustrated that it can indeed be differentiated between an 'of f-state', which possesses no 'through-conjugation' of the K-donor subs tituent and the corresponding MeOCO group and an 'on-state' where this 'through-conjugation' is realized. The 'through-conjugation', i.e., c onjugative interaction via the involved s-cis-butadiene substructure o f the heptalene skeleton, is indicated by a strong enhancement of the intensities of the heptalene absorption bands I and II (cf: Tables 36) . The most impressive examples are the heptalene-dicarboxylates 11a, r epresenting the off-stale, and 11b which stands for the on-state (cf: Fig. 8).