Alcohol Solvates of Lanthanoid(III) Trifluoromethanesulfonates

After vacuum dehydration, a number of hydrated trivalent lanthanoid trifluoromethanesulfonates (“triflate”, “OTf” = F3CSO3), when recrystallized from various alcohol (ROH) solutions, yield solvates Ln(OTf)3·xROH, x = 3, 5 or 6. The following have been defined crystallographically (R/Ln/x): Me/La/3;Me/Gd/6; Et/Sm/3; Et/Gd/5 iPr/Nd,Sm/3. The Me/Gd/6complex, Gd(OTf)3·6MeOH is a mononuclear/ionic form [(MeOH)6Gd(O–OTf)2](OTf), the gadolinium environment being octacoordinate, square-antiprismatic with the O–OTf donors quasi-trans on different faces of the coordination polyhedron; the Et/Gd/5 complex is neutral, molecular, mononuclear [(EtOH)5Gd(O–OTf)3], also with an octacoordinate, square-antiprismatic coordination sphere, derivative of that of the methanol solvate. The remainder form one-dimensional polymeric arrays, successive lanthanoid atoms linked by (μ-O–OTf–O′)3 triads, at either end of a tricapped trigonal prismatic array, the ROH molecules contributing the capping atoms. A (“baseline”) (re-)determination of the “parent” Sm(OTf)3·9H2O is also recorded.