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Helicate Extension as a Route to Molecular Wires
Author(s) -
Schultz David,
Biaso Frédéric,
Shahi Abdul Rehaman Moughal,
Geoffroy Michel,
Rissanen Kari,
Gagliardi Laura,
Cramer Christopher J.,
Nitschke Jonathan R.
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800503
Subject(s) - copper , delocalized electron , amine gas treating , electrochemistry , ion , diamine , chemistry , aldehyde , metal , materials science , metal ions in aqueous solution , crystallography , combinatorial chemistry , polymer chemistry , electrode , organic chemistry , catalysis
Abstract 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”.