Abstract
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.
Highlights
Over the past decades, borates have attracted burgeoning attention owning to their excellent properties and wide applications such as non-linear optical (NLO) materials, birefringent materials, electrode materials, etc [1,2,3,4,5,6,7]
3(ZnB5O10)PO4 was successfully synthesized as the first DUV NLO zincoborate-phosphate
The thermal expansion behavior of Zn4B6O13 between 13 and to 270 K was investigated by the variable-temperature X-ray diffraction (XRD) and variation of refined cell parameters
Summary
Borates have attracted burgeoning attention owning to their excellent properties and wide applications such as non-linear optical (NLO) materials, birefringent materials, electrode materials, etc [1,2,3,4,5,6,7]. Molecules 2019, 24, 2763 are composed of [B3 O6 ]3− and [B3 O7 ]5− groups, respectively These FBBs, in turn, may polymerize to form isolated clusters, infinite one-dimensional (1D) chains, two-dimensional (2D) layers or three-dimensional (3D) frameworks, which endow borates with rich structural chemistry and extensive applications [18,19,20,21]. In the last few decades, borates containing zinc cations have become a research focus and zincoborates with novel structures or good properties were continuously reported [55,56,57]. In recent years, using Zn2+ to substitute Be2+ in the KBBF family has been proved to be a rational design strategy to synthesize desired compounds with KBBF-type layered structures, which is an effective way to explore new UV/DUV NLO materials. Structural reported, whichChemistry are rarely found in borates, implying the special role of zinc cations in regulating and controlling the B-O configuration
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