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J Am Chem Soc. 2012 Oct 03;134(39):16289-97. doi: 10.1021/ja306212m. Epub 2012 Sep 20.

Deposition of ordered layers of tetralactam macrocycles and ether rotaxanes on pyridine-terminated self-assembled monolayers on gold.

Journal of the American Chemical Society

Sebastian Richter, Johannes Poppenberg, Christoph H-H Traulsen, Erik Darlatt, Anja Sokolowski, Dominik Sattler, Wolfgang E S Unger, Christoph A Schalley

Affiliations

  1. Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany.

PMID: 22947111 DOI: 10.1021/ja306212m

Abstract

The deposition of tetralactam macrocycles and the corresponding benzyl ether rotaxanes on gold substrates is investigated for the first time exploiting metallo-supramolecular chemistry. Two pyridine-terminated self-assembled monolayers (SAMs) are developed that are used as well-ordered template layers. The two SAMs differ with respect to the rigidity of the terminal pyridines as shown by angle-resolved near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The template layers are then used for the metal-mediated self-assembly of macrocylces and rotaxanes on solid supports. The SAM with the more rigid terminal pyridine shows a higher coverage with the macrocycles and is therefore preferable. Angle-resolved NEXAFS spectroscopy also shows the deposited supramolecules to be oriented preferentially upright. This order is only achieved for the macrocycles through the deposition on the more rigid SAM template, whereas rotaxanes form oriented layers on both SAMs. Time-of-flight secondary-ion mass spectrometry analysis was used to determine the deposition time required for the self-assembly process.

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