On‐Surface Domino Reactions: Glaser Coupling and Dehydrogenative Coupling of a Biscarboxylic Acid To Form Polymeric Bisacylperoxides. Issue 33 (13th July 2016)

• Record Type: Journal Article
• Authors: Held, Philipp Alexander; Gao, Hong‐Ying; Liu, Lacheng; Mück‐Lichtenfeld, Christian; Timmer, Alexander; Mönig, Harry; Barton, Dennis; Neugebauer, Johannes; Fuchs, Harald; Studer, Armido
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 33(2016)
• Page Start: 9777
• Page End: 9782
• Publication Date: 2016-07-13
• Subjects: Glaser coupling -- gold -- scanning tunneling microscopy -- self-assembly -- surface chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201602859
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Herein we report the on‐surface oxidative homocoupling of 6, 6′‐(1, 4‐buta‐1, 3‐diynyl)bis(2‐naphthoic acid) (BDNA) via bisacylperoxide formation on different Au substrates. By using this unprecedented dehydrogenative polymerization of a biscarboxylic acid, linear poly‐BDNA with a chain length of over 100 nm was prepared. It is shown that the monomer BDNA can be prepared in situ at the surface via on‐surface Glaser coupling of 6‐ethynyl‐2‐naphthoic acid (ENA). Under the Glaser coupling conditions, BDNA directly undergoes polymerization to give the polymeric peroxide (poly‐BDNA) representing a first example of an on‐surface domino reaction. It is shown that the reaction outcome varies as a function of surface topography (Au(111) or Au(100)) and also of the surface coverage, to give branched polymers, linear polymers, or 2D metal–organic networks. Abstract : Playing dominos on gold : 6‐Ethynyl‐2‐naphthoic acid (ENA) undergoes on‐surface Glaser coupling on gold to form 6, 6′‐(1, 4‐buta‐1, 3‐diynyl)bis(2‐naphthoic acid) (BDNA) which in turn reacts in an unprecedented dehydrogenative coupling of the acid functionalities to give poly‐BDNA. Polymeric chains with a length of over 100 nm can be obtained and the reaction outcome is influenced by the Au‐surface topography and the surface coverage.