Helicate Extension as a Route to Molecular Wires

Schultz, D.; Biaso, F.; Moughal Shahi, A. R.; Geoffroy, M.; Rissanen, K.; Gagliardi, L.; Cramer, C. J.; Nitschke, J.
Chem. Eur. J. 2008, 14, 7180.

We describe the preparation of a helicate containing four closely-spaced, linearly-arrayed copper(I) ions. This product may be prepared either directly by mixing copper(I) with a set of precursor amine and aldehyde subcomponents, or indirectly via the dimerization of a dicopper(I) helicate upon addition of 1,2-phenylenediamine. A notable feature of this helicate is that its length is not limited by the lengths of its precursor subcomponents: each of the two ligands wrapped around the four copper(I) centers contains one diamine, two dialdehyde and two monoamine residues. This work thus paves the way for the preparation of longer oligomeric and polymeric structures. Density Functional Theory calculations and electrochemical measurements indicate a high degree of electronic delocalization among the metal ions forming the cores of the structures described herein, which may therefore be described as "molecular wires".

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