Rare earth(III) β-diketonates are highly remarkable
luminophores
in the visible spectral region among the rare earth compounds, owing
to the efficient contribution from the 4f–4f intraconfigurational
transitions. To get detailed structural insight into the RE3+ sites (RE = Eu, Gd, and Sm), X-ray absorption near-edge spectroscopy
(XANES) can be very potent in probing the local chemical environment
around the RE3+ ion. In this work, a PyFitIt machine learning
approach was employed as a new strategy to simulate the Eu, Gd, and
Sm L3-edge XANES and thereby determine the local atomic
structure of the luminescence RE3+ β-diketonate complexes,
[Eu(tta)3(H2O)2], [C4mim][Eu(dbm)4], [Gd(tta)3(H2O)2], and
[Sm(dbm)3(phen)] (tta, 3-thenoyltrifluoroacetonate; dbm,
dibenzoylmethane; phen, phenanthroline; and C4mim, 1-butyl-3-methylimidazolium
bromide). Continuous Cauchy wavelet transform validated the PyFitIt
calculated XANES by visualizing very efficiently the coordination
geometries, composed of O and O/N backscatterers around the RE3+ (RE = Eu and Gd) and Sm3+ ions, respectively,
as a pinkish-red color map in the two-dimensional images of the corresponding
complexes. Extended X-ray absorption fine structure fit in Artemis
also corroborated the three-dimensional structures generated by PyFitIt
XANES simulation for all the compounds. Though, relatively slightly
higher bond distance values for the Sm3+ complex are due
to the higher atomic radius of the Sm3+ ion when compared
to the Eu3+ and Gd3+ complexes. Meanwhile, higher
Debye–Waller factor (σ2) values for the [C4mim][Eu(dbm)4] when compared to the [Eu(tta)3(H2O)2] indicated the structure disorder,
owing to the distortion in the local geometry. It is noteworthy that
the optical properties, described mainly by the Ωλ (λ = 2 and 4) 4f–4f intensity parameters, are very
sensitive to the local coordination environment around the Eu3+ ion. Thus, a close agreement between the experimental and
theoretically calculated Ωλ parameter values
confirmed that the PyFitIt calculated square antiprismatic structures
are precisely similar to the real structures of the Eu3+ complexes.