The mechanisms of the solid state polymerization reactions in diacetylene crystals have been investigated by ESR-spectroscopy. The electronic structure of the diradical, carbene and dicarbene intermediates of the low-temperature photopolymerization reaction of diacetylene crystals have been analyzed. From the chain-lengths dependent ESR fine structure and from the isotropic hyperfine structure detailed information concerning the radical and carbene wavefunctions were deduced. A multiplicity change from S=1 to S=2 occurs at the hexamer intermediates.
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Sixl et al. (1984) studied this question.
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