Insights About the Mechanism of the Formation of Supramolecular π‐Stacked Rectangles Based on Cu<sup>I</sup> Bimetallic Complexes Bearing a Bridging Phosphane Ligand

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Published
2013-11-15
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DOI
  • 10.1002/ejic.201301209
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Wiley

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<jats:title>Abstract</jats:title><jats:p>The variation in the ratio of the reactants in the supramolecular self‐assembly reaction of the bimetallic Cu<jats:sup>I</jats:sup> “U‐shaped” molecular clip <jats:bold>1</jats:bold> with the 1,4‐dicyanobenzene <jats:bold>3</jats:bold> and the 1,8‐anthracene‐9,10‐carbonitrile <jats:bold>4</jats:bold> “short” ditopic ligand have allowed the observation of new “open” supramolecular assemblies <jats:bold>7</jats:bold> and <jats:bold>8</jats:bold>, respectively, in addition to the previously characterized π‐stacked supramolecular rectangles <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold>, respectively. These new derivatives have been characterized by their solid‐state structure obtained by X‐ray diffraction on single crystals and by NMR spectroscopy in the case of derivative <jats:bold>7</jats:bold>. Depending on the extent of the π system included in the core of the homoditopic linker, different behaviors are observed. In the case of derivative <jats:bold>7</jats:bold> based on the “phenyl” linker <jats:bold>3</jats:bold>, a 1:1 <jats:bold>1</jats:bold>/<jats:bold>3</jats:bold> ratio affords the open derivative in a good yield, whereas a 1:0.5 <jats:bold>1</jats:bold>/<jats:bold>4</jats:bold> ratio allows the isolation of derivative <jats:bold>8</jats:bold> in very low yield. These results allow for a tentative analysis of the mechanism that occurs along with the supramolecular self‐assembly processes to afford π‐stacked supramolecular rectangles.</jats:p>

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