Our group has focused previously on the use of thiacrown ethers in the synthesis of supramolecular complexes, such as squares and triangles.  In this report, our research is expanded to include azacrown ethers in Pt(II) and Pd(II) complexes.  Molecular squares and triangles are synthesized using a tridentate macrocyclic capping ligand (1,4,7-trithiacyclononane, 1,4,7-triazacyclononane, or 1,4,7-trimethyl-1,4,7-triazacyclononane) on a square planar Pt(II) or Pd(II) complex.  The macrocycle occupies two cis coordination sites with its third donor in an axial position on the metal ion and forms a corner of the polygon. Next, the corners are linked into a polygon using linear diimine ligands such as 4,4'-bipyridine. The polygon is formed from three components -- the capping macrocyclic ligand, the d8 metal center, and the linear linker. Several complexes show evidence of both square and triangle formation through NMR and ESI-MS data.  Also, NMR evidence points to an equilibrium between the two polygons.

Synthesis of Pt(II) and Pd(II) molecular squares and triangles using thiacrowns and azacrowns as capping ligands

243rd National Meeting (2012)

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