Lanthanide(III)
Complexation with an Amide Derived
Pyridinophane
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Abstract
Herein we report a detailed investigation
of the solid state and solution structures of lanthanide(III) complexes
with the 18-membered pyridinophane ligand containing acetamide pendant
arms TPPTAM (TPPTAM = 2,2′,2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide).
The ligand crystallizes in the form of a clathrated hydrate, where
the clathrated water molecule establishes hydrogen-bonding interactions
with the amide NH groups and two N atoms of the macrocycle. The X-ray
structures of 13 different Ln<sup>3+</sup> complexes obtained as the
nitrate salts (Ln<sup>3+</sup> = La<sup>3+</sup>–Yb<sup>3+</sup>, except Pm<sup>3+</sup>) have been determined. Additionally, the
X-ray structure of the La<sup>3+</sup> complex obtained as the triflate
salt was also obtained. In all cases the ligand provides 9-fold coordination
to the Ln<sup>3+</sup> ion, ten coordination being completed by an
oxygen atom of a coordinated water molecule or a nitrate or triflate
anion. The bond distances of the metal coordination environment show
a quadratic change along the lanthanide series, as expected for isostructural
series of Ln<sup>3+</sup> complexes. Luminescence lifetime measurements
obtained from solutions of the Eu<sup>3+</sup> and Tb<sup>3+</sup> complexes in H<sub>2</sub>O and D<sub>2</sub>O point to the presence
of a water molecule coordinated to the metal ion in aqueous solutions.
The analysis of the Ln<sup>3+</sup>-induced paramagnetic shifts indicates
that the complexes are ten-coordinated throughout the lanthanide series
from Ce<sup>3+</sup> to Yb<sup>3+</sup>, and that the solution structure
is very similar to the structures observed in the solid state. The
complexes of the light Ln<sup>3+</sup> ions are fluxional due to a
fast Δ(λλλλλλ) ↔
Λ(δδδδδδ) interconversion
that involves the inversion of the macrocyclic ligand and the rotation
of the acetamide pendant arms. The complexes of the small Ln<sup>3+</sup> ions are considerably more rigid, the activation free energy determined
from VT <sup>1</sup>H NMR for the Lu<sup>3+</sup> complex being Δ<i>G</i><sup>⧧</sup><sub>298</sub> = 72.4 ± 5.1 kJ
mol<sup>–1</sup>