Studies of The Soltd State Reactivity and Properties of Diacetylene Polymers and Acetylenes

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Abstract
The physical considerations which motivate our interest in fully crystalline polymers derived from acetylenic and diacetylenic monomers are presented. The interaction of the polymer derived from 1,6-di-N-carbazolyl-2,4-hexadiyne (DCH) with antimony pentahalides (SbX5, X=F, Cl) has been studied as a function of polymerization method. It was found that thermally polymerized DCH takes up SbX5, and the chemical, spectral, crystallographic, and electrical properties of the resultant material are reported. The reactivity in the solid state of the simple hydrogen bonded acetylenes propiolamide and the oxime and semicarbazone of propiolaldehyde using heat and 60Co gamma radiation as stimuli has been studied. While the above acetylenes are unreactive to gamma radiation in comparison to diacetylenes and metal propiolates, their reactivity was enhanced when they were crystallized from chlorinated solvents. Propiolaldehyde semicarbazone is monoclinic, space group P2/n, a = 10.582(3), b = 3.801(1), c = 14.065(4)Å; β = 109.02(3)° Z = 4. Solved by direct methods, the structure reveals stacks along b and important acetylenic carbon-carbon contacts at less than 3.80Å. Several possible considerations relevant to structure-reactivity relationships and mechanistic aspects of reaction initiation are discussed.

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