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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

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posted on 2016-09-02, 16:18 authored by Marina A. Polovkova, Alexander G. Martynov, Kirill P. Birin, Sergey E. Nefedov, Yulia G. Gorbunova, Aslan Yu. Tsivadze
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.

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