Hexacene is very unstable, being highly reactive in the 6, 15 positions due to pi electron localization. Its spectra must be collected on freshly purified samples handled in an inert atmosphere such as nitrogen or argon. Only with very large substituents it is possible to isolate an hexacene for instance the compound 6,15-bis(tri-t-butylsilylethynyl)hexacene which melts with decomposition at 96°C.
The first reported synthesis of hexacene itself dates back to 1942 In 1955 the compound is synthesized by dehydrogenation of hexacosadehydrohexacene by palladium on carbon . In 1982 hexacene is reported as a bluish green compound with decomposition at 380 degrees . In 2007, a research group claimed the first reproducible unsubstituted hexacene synthesis (invalidating the previous claims) based on photochemical decarbonylation of a dione precursor :
The compound cannot be isolated: it dimerizes even at concentration as low as 10-4 M and reacts in solution with oxygen to the organic peroxide. In a PMMA polymer matrix on the other hand these side-reactions are limited and the compound can survive up to 12 hours. The next homologue heptacene also studied by this group, is even more unstable (decomposes within 4 hours).