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Perfluorophenyl–Phenyl Interactions in the Crystallization and Topochemical Polymerization of Triacetylene Monomers
Author(s) -
Xu Rui,
Schweizer W. Bernd,
Frauenrath Holger
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900985
Subject(s) - polymerization , monomer , polymer , crystallization , raman spectroscopy , polymer chemistry , crystallography , crystal structure , materials science , solid state , crystal (programming language) , chemistry , organic chemistry , programming language , physics , computer science , optics
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 perfluorophenyl–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 polymerization. Raman as well as solid‐state 13 C NMR spectra of the obtained polymers revealed that the polymerization had predominantly proceeded in the form of a 1,4‐polyaddition.