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Issue 11, 2006
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Addressing metal centres in supramolecular assemblies

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Abstract

Supramolecular metal ion assemblies are deposited from their solutions onto highly orientated pyrolytic graphite (HOPG) substrates to be imaged by scanning tunnelling microscopy (STM). Since the structural and electronic information of STM measurements are strongly entangled, the spectroscopic interpretation and analysis of the images of such molecular assemblies has proven to be challenging. This tutorial review focuses on a general room temperature scanning tunnelling spectroscopy (STS) protocol, current induced tunnelling spectroscopy (CITS), applied to free-standing 1D and 2D arrangements of supramolecular metal ion assemblies rendering local tunnelling probabilities with submolecular resolution. The size of the investigated molecular assemblies was confirmed by comparison with X-ray crystallographic data, while the consistency of the spectroscopic investigations and of the determined positions of the metal ions within the assemblies was checked by DFT calculations. Due to the genuine level structure of coordinated metal centers, it was possible to map exclusively the position of the coordination bonds in supramolecular transition metal assemblies with submolecular spatial resolution using the CITS technique. CITS might thus constitute an important tool to achieve directed bottom-up construction and controlled manipulation of fully electronically functional, two-dimensional molecular designs.

Graphical abstract: Addressing metal centres in supramolecular assemblies

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Publication details

The article was received on 10 Aug 2006 and first published on 11 Sep 2006


Article type: Tutorial Review
DOI: 10.1039/B517267P
Citation: Chem. Soc. Rev., 2006,35, 1056-1067

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    Addressing metal centres in supramolecular assemblies

    M. Ruben, J. Lehn and P. Müller, Chem. Soc. Rev., 2006, 35, 1056
    DOI: 10.1039/B517267P

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