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; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– 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.