Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties

Borates have been regarded as a rich source of functional materials due to their diverse structures and wide applications. Therein, zincobrates have aroused intensive interest owing to the effective structural and functional regulation effects of the strong-bonded zinc cations. In recent decades, numerous zincoborates with special crystal structures were obtained, such as Cs₃Zn₆B₉O₂₁ and AZn₂BO₃X₂ (A = Na, K, Rb, NH₄; X = Cl, Br) series with KBe₂BO₃F₂-type layered structures were designed via substituting Be with Zn atoms, providing a feasible strategy to design promising non-linear optical materials; KZnB₃O₆ and Ba₄Na₂Zn₄(B₃O₆)₂(B₁₂O₂₄) with novel edge-sharing [BO₄]^5- tetrahedra were obtained under atmospheric pressure conditions, indicating that extreme conditions such as high pressure are not essential to obtain edge-sharing [BO₄]^5--containing borates; Ba₄K₂Zn₅(B₃O₆)₃(B₉O₁₉) and Ba₂KZn₃(B₃O₆)(B₆O₁₃) comprise two kinds of isolated polyborate anionic groups in one borate structure, which is rarely found in borates. Besides, many zincoborates emerged with particular physicochemical properties; for instance, Bi₂ZnOB₂O₆ and BaZnBO₃F are promising non-linear optical (NLO) materials; Zn₄B₆O₁₃ and KZnB₃O₆ possess anomalous thermal expansion properties, etc. In this review, the synthesis, crystal structure features and properties of representative zincoborates are summarized, which could provide significant guidance for the exploration and design of new zincoborates with special structures and excellent performance.