Alcohol Solvates of Lanthanoid(III) Trifluoromethanesulfonates

After vacuum dehydration, a number of hydrated trivalent lanthanoid trifluoromethanesulfonates (“triflate”, “OTf” = F 3 CSO 3 ), 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 i Pr/Nd,Sm/3. The Me/Gd/6complex, Gd(OTf) 3 · 6MeOH is a mononuclear/ionic form [(Me O H) 6 Gd( 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) 5 Gd( 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 R O H molecules contributing the capping atoms. A (“baseline”) (re‐)determination of the “parent” Sm(OTf) 3 · 9H 2 O is also recorded.