Croconato-containing M(III) (M = Ga, Er) complexes as potential building blocks for mono/multifunctional molecular materials

The one-pot synthesis and structural characterization of two new complexes of the croconato ligand (C5O5)2− with the Ga(III) and Er(III) metal ions are reported. The mononuclear tris-chelated (n-Bu4N)3[Ga(C5O5)3], 1, which exhibits an octahedral geometry, is present as Δ and Λ enantiomers in equal amounts; the K2[Er(C5O5)(μ-SO4)(OH2)4]2 complex, 2, shows dinuclear erbium moieties with bridging sulfate anions and interposed K(I) cations with a capped trigonal prismatic coordination geometry. 2 shows paramagnetic behavior in the 2–300 K range typical of two isolated Er(III) ions. Vibrational (FT-IR and FT-Raman) and electronic spectroscopies have shown to be a reliable diagnostic tool in distinguishing different molecular arrangements of the croconato ligand in different complexes. The analogies of the gallium complex with the corresponding [M(C2O4)3]3− tris-chelated complexes which have been used as chiral building blocks of molecular conductors are pointed out.

Graphical abstractThe easy one-pot synthesis and first X-ray structures of mononuclear and polynuclear Ga(III) and Er(III) complexes with the croconate ligand are reported. The gallium complex is analog of the corresponding [M(ox)3]3− tris-chelated complexes (ox = oxalato) which have been used as chiral building blocks of BEDT-TTF (bis(ethylenedithio)tetrathiafulvalene)-based molecular conductors and superconductors; the polynuclear erbium complex, given its optical and magnetic properties, may have the potential to build multifunctional molecular materials.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► One-pot synthesis and first X-ray structure of croconato-based M(III) (M = Ga, Er) complexes. ► The gallium complex have the potential to build chiral molecular (super)conductors. ► The polynuclear erbium complex have the potential to build multifunctional materials. ► Vibrational and electronic spectroscopies are diagnostic in distinguishing croconato arrangements in transition metal complexes.