Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a
general and convenient approach to the synthesis of heteronuclear
crown-substituted triple-decker phthalocyaninates afforded two series
of complexes containing one dia- and one paramagnetic Ln­(III) ion
(for Y and almost the whole lanthanide family), [(15C5)4Pc]­M*­[(15C5)4Pc]­M­(Pc) (or [M*,M] for brevity sake), where
(15C5) is 15-crown-5; (Pc2–) is phthalocyaninato
dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This
approach consists of using LaPc2 as an efficient Pc2– source. The solid-state structures of two complexes
([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction
analysis, providing therefore a structural model for the assignment
and analysis of 1H NMR spectra of the complexes, which
is strongly affected by the presence of paramagnetic lanthanide ions.
Model validation was performed on complexes containing two different
paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm]
and [Tm*,Tb]synthesized by the above-mentioned method.