Ln(OC6F5)(3) form stable, isolable compounds with 1,2-dimethoxyethane (DME). Monomeric (DME)(2)Ln(OC6F5)(3) (Ln Nd, Er, Tm) adopt seven coordinate structures with two chelating DME and three terminal phenoxide ligands. Both (py)(4)Er(OC6F5)(3) and (THF)(3)Yb(OC6F5)(3) were also prepared and structurally characterized, with the latter being a mer-octahedral compound with bond lengths that are geometry dependent. Emission experiments on crystalline powders of the Nd(III), Tm(III), and Er(III) DME derivatives show that these compounds are highly emissive near-infrared sources.