Helicate extension as a route to molecular wires.
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 through 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 oligo- and polymeric structures. DFT 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".
Schultz
David
D
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, Geneva, Switzerland.
Biaso
Frédéric
F
Shahi
Abdul Rehaman Moughal
AR
Geoffroy
Michel
M
Rissanen
Kari
K
Gagliardi
Laura
L
Cramer
Christopher J
CJ
Nitschke
Jonathan R
JR