The heptadentate N4O3 ligand called TRAC has been known since the late 1980s and can be described as three β-ketoiminates tethered together with an amine linker. Remarkably, this heptadentate ligand has been used to prepare lanthanide complexes with Ln = Sm, Er, and Yb that can be sublimed intact at 180 °C at 10-2 Torr (J. Am. Chem. Soc. 1991, 113, 2528-2532). Since the initial discovery of lanthanide TRAC complexes, little has been reported on how various electronic and steric changes to the ligand affect the volatility and thermal stability of lanthanide complexes. Here we describe the synthesis, structures, and thermal properties for a series of lanthanide complexes with three different fluorinated TRAC ligands bound to Nd, Er, and/or Yb. Single-crystal XRD and NMR data will be reported along with thermogravimetric analysis (TGA) data that shows how fluorination can dramatically increase the volatility of lanthanide TRAC complexes. Potential applications will be discussed.

Synthesis and thermal properties of lanthanide complexes with fluorinated heptadentate β-ketoiminate ligands

ACS Fall 2021

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