Perfluorophenyl–Phenyl Interactions in the Crystallization and Topochemical Polymerization of Triacetylene Monomers

摘要

A series of symmetrically and unsymmetrically substituted octa-2,4,6-triyne-1,8-diol derivatives with benzoyl, 4-dodecyloxybenzoyl, as well as perfluorobenzoyl substituents were prepared and investigated with respect to their crystal structures and topochemical polymerizability. Single-crystal structures for several of these triacetylene monomers have been obtained and proved that the perfluorophenyl–phenyl interactions played a decisive role in the molecular packing. As a consequence of the geometric requirements imposed by the erfluorophenyl– phenyl interactions, packing parameters appropriate for a topochemical triacetylene polymerization in the sense of either a 1,6- or a 1,4-polyaddition along different crystallographic axes were observed in two cases, and UV irradiation led to successful olymerization. Raman as well as solidstate 13C NMR spectra of the obtained polymers revealed that the polymerization had predominantly proceeded in the form of a 1,4-polyaddition.