Three Polyborates with High-Symmetry [B₁₂O₂₄] Units Featuring Different Dimensions of Anion Groups

Three polyborates, namely, LiNa₁₁B₂₈O₄₈, Li_1.45Na_7.55B₂₁O₃₆, and Li₂Na₄Ca₇Sr₂B₁₃O₂₇F₉, were synthesized via the high-temperature solution method. All of them feature high-symmetry [B₁₂O₂₄] units, yet their anion groups exhibit distinct dimensions. LiNa₁₁B₂₈O₄₈ features a three-dimensional anionic structure of ³[B₂₈O₄₈]_∞ framework, which is composed of three units: [B₁₂O₂₄], [B₁₅O₃₀], and [BO₃]. Li_1.45Na_7.55B₂₁O₃₆ possesses a one-dimensional anionic structure of ¹[B₂₁O₃₆]_∞ chain consisting of [B₁₂O₂₄] and [B₉O₁₈] units. The anionic structure of Li₂Na₄Ca₇Sr₂B₁₃O₂₇F₉ is composed of two zero-dimensional isolated units, namely, [B₁₂O₂₄] and [BO₃]. The novel FBBs [B₁₅O₃₀] and [B₂₁O₃₉] are present in LiNa₁₁B₂₈O₄₈ and Li_1.45Na_7.55B₂₁O₃₆, respectively. The anionic groups in these compounds exhibit a high degree of polymerization, thereby augmenting the structural diversity of borates. And the crystal structure, synthesis, thermal stability, and optical properties were meticulously discussed to guide the synthesis and characterization of novel polyborates.