Journal of the American Chemical Society 2014-07-09

Decarboxylative polymerization of 2,6-naphthalenedicarboxylic acid at surfaces.

Hong-Ying Gao, Philipp Alexander Held, Marek Knor, Christian Mück-Lichtenfeld, Johannes Neugebauer, Armido Studer, Harald Fuchs

Index: J. Am. Chem. Soc. 136(27) , 9658-63, (2014)

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Abstract

Metal-catalyzed polymerization of 2,6-naphthalenedicarboxylic acid (NDCA) to form poly-2,6-naphthalenes at various surfaces is reported. Polymerizations occur via initial formal dehydrogenation of self-assembled diacids with subsequent decarboxylation to give polymeric bisnaphthyl-Cu species at elevated temperature as intermediate structures (<160 °C). Further temperature increase eventually leads to poly-naphthalenes via reductive elimination. It is demonstrated that the Cu(111) surface works most efficiently to conduct such polymerizations as compared to the Au(111), Ag(111), Cu(100), and Cu(110) surfaces. Poly-2,6-naphthalene with a chain length of over 50 nm is obtained by using this approach. The decarboxylative coupling of aromatic diacids is a very promising tool which further enlarges the portfolio of reactions allowing for on-surface polymerizations and novel organometallic systems preparations.