Two Structure Types Based on Si6O15 Rings: Synthesis and Structural and Spectroscopic Characterisation of Cs1.86K1.14DySi6O15 and Cs1.6K1.4SmSi6O15

Abstract The silicate Cs1.86K1.14DySi6O15 represents a mixed tetrahedral‐octahedral framework structure type based on roughly circular Si6O15 rings and isolated DyO6 octahedra. The silicate Cs1.6K1.4SmSi6O15 has a layered atomic arrangement built from corrugated Si6O15 layers containing four‐, six‐ and eight‐membered rings. The layers are connected by isolated SmO6 octahedra to form a mixed tetrahedral‐octahedral framework. This structure shows a close structural relationship to β‐K3NdSi6O15 and a less close one to dehydrated elpidite (Na2ZrSi6O15). In both structures, Cs/K atoms occupy large voids. The silicates were obtained through high‐temperature flux syntheses. Their crystal structures have been determined from single‐crystal X‐ray diffraction data. Cs1.86K1.14DySi6O15 crystallises in R32 (no. 155) with a = 13.896(2), c = 35.623(7) Å and V = 5957.2(17) Å3, whereas Cs1.6K1.4SmSi6O15 crystallises in Cmca (no. 64) with a = 14.474(3), b = 14.718(3), c = 15.231(3) Å and V = 3244.7(11) Å3. The Dy3+ and Sm3+ cations present in the silicates cause PL emission bands in the visible yellow‐to‐orange spectral range.