Products Cited in Publications Worldwide Understanding the Coordination Chemistry and Structural and Photophysical Properties of EuII-and SmII-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines

Understanding the Coordination Chemistry and Structural and Photophysical Properties of EuII-and SmII-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines

Bokouende, Sergely Steephen; Ward, Cassandra L; Allen, Matthew J

DOI: PMID:

Abstract

Ligands play a crucial role in supporting or stabilizing the divalent oxidation state of lanthanide metals. To expand the range of ligands used to chelate divalent lanthanide ions, we synthesized and studied the structural and photophysical properties of complexes of EuII and SmII with hexamethylhexacyclen, , , and as supporting ligands. Coordination of hexamethylhexacyclen, an analogue of , generates sterically crowded complexes of EuII and SmII that are either seven or eight coordinate and adopt a range of geometries that differ from those of their 18- crown-6 counterparts and from those of lanthanide-containing complexes with the acyclic tetradente tertiary amine ligands included in this report. The emission spectra of EuII(hexamethylhexacyclen) show a moderate sensitivity to counterion identity and are more red-shifted compared to those of complexes of EuII with and the hexamethylated aza derivative of 2.2.2-cryptand. In addition, the morphology of hexamethylhexacyclen in [LnI- (hexamethylhexacyclen)]I was found to resemble that of thermally stable alkalides of the form [M(hexamethylhexacyclen)]Na− (M = K+ or Cs+), suggesting that hexamethylhexacyclen could be an interesting ligand for strongly reducing lanthanide ions.

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Hexacyclen

A697313296-35-595%

Hexacyclen

88.0/100mg

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