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J Am Chem Soc. 2016 Dec 7;138(48):15580-15586. Epub 2016 Nov 23.

Hexagons to Ribbons: Flipping Cyanide on Au{111}.

Author information

1
California NanoSystems Institute, University of California, Los Angeles , Los Angeles, California 90095, United States.
2
Department of Chemistry and Biochemistry, University of California, Los Angeles , Los Angeles, California 90095, United States.
3
Department of Material Science and Engineering, University of California, Los Angeles , Los Angeles, California 90095, United States.
4
Department of Mathematics, University of California, Los Angeles , Los Angeles, California 90095, United States.
5
Department of Industrial Engineering and Management Sciences, Northwestern University , Evanston, Illinois 60208, United States.
6
Department of Physics, University of California , Santa Barbara, California 93106, United States.
7
Department of Mathematics, University of San Francisco , San Francisco, California 94117, United States.
8
Department of Mathematics and Natural Sciences, California State University , Long Beach, California 90840, United States.
9
Department of Mathematics, Laboratoire Jacques Louis Lions, Université Paris Diderot , 5 Rue Thomas Mann, Paris 75013, France.
10
Department of Mathematics and Statistics, San Diego State University , San Diego, California 92182, United States.
11
Department of Chemistry, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
12
Applied Physical Chemistry, Heidelberg University , 69120 Heidelberg, Germany.

Abstract

Cyanide monolayers on Au{111} restructure from a hexagonal close-packed lattice to a mixed-orientation "ribbon" structure through thermal annealing. The new surface structure loses most of the observed surface features characterizing the initial as-adsorbed system with "ribbon" domain boundaries isolating rotationally offset surface regions where the orientation is guided by the underlying gold lattice. A blue shift to higher frequencies of the CN vibration to 2235 cm-1 with respect to the as-adsorbed CN/Au{111} vibration at 2146 cm-1 is observed. In addition, a new low-frequency mode is observed at 145 cm-1, suggesting a chemical environment change similar to gold-cyanide crystallization. We discuss this new structure with respect to a mixed cyanide/isocyanide monolayer and propose a bonding scheme consisting of Au-CN and Au-NC bound molecules that are oriented normal to the Au{111} surface.

PMID:
27934033
DOI:
10.1021/jacs.6b06046
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