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Pure Appl. Chem., 2007, Vol. 79, No. 6, pp. 1077-1085

Self-assembly of a nickel(II) pseudorotaxane nanostructure on a gold surface

Agnieszka Więckowska1, Marta Wiśniewska1, Marcin Chrzanowski2, Jarosław Kowalski3, Bohdan Korybut-Daszkiewicz2,3 and Renata Bilewicz1

1 Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
2 Department of Mathematics and Natural Science, College of Science, Cardinal Stefan Wyszyński University, Dewajtis 5, 01-815 Warsaw, Poland
3 Institute of Organic Chemistry Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

Abstract: Tetraazamacrocyclic complexes of NiII and CuII can be used as components of catenanes or rotaxanes showing electrochemically switched intramolecular motion in solution. In our present studies, we modify these compounds with organothiol chains to attach them to the surface of the electrode using the self-assembly method and employ them next as molecular switches, which change conductivity upon applying appropriate potential. The electrochemical properties of these compounds are studied in the solution and, in the case of thiol derivative, immobilized on the electrode surface. The macrocyclic complex of NiII, immobilized on the Au surface, forms the axis of the rotaxane. This compound can be anchored to the surface by one or two thiol groups. The data obtained from scanning tunneling microscopy (STM) experiments using colloidal Au confirm that the orientation normal to the surface dominates. The electrochemical experiments reveal reversible one-electron oxidation of metal center from +2 to +3. The behavior of the electrode modified with the macrocyclic complex of NiII upon immersion in a solution containing bismacrocyclic complex of NiII points to the formation of a new rotaxane-like nanostructure on the surface of the electrode.