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Hexacene was the largest acene obtained and characterized in the last century, followed by heptacene in 2006. Since then, a race for obtaining the largest acene resulted in the development of several members of this family as well as diverse innovative synthetic strategies, from solid\u2010state chemistry to the promising on\u2010surface chemistry. This last technique allows the obtention of large acenes, up to tridecacene, the largest acene so far. 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