Ba₃(BO₃)(CO₃)F: The First Borate Carbonate Fluoride Synthesized by the High‐Temperature Solution Method

Abstract

In contrast to the well‐investigated halogen‐containing borates and carbonates, very few halogen‐containing borate carbonate compounds have been reported. Specifically, no example of borate carbonate fluoride has been synthesized successfully until now. Herein, the planar π‐conjugated units [BO3]3− and [CO3]2− and the F− ions are introduced simultaneously into one crystal structure resulting in the first borate carbonate fluoride, Ba3(BO3)(CO3)F, by the high‐temperature solution method in the atmosphere. Its structure features a hexagonal channel formed by the [BO3]3− and [CO3]2− units with the [F3Ba8]13+ trimers filled in the channel. Various characterizations including single crystal‐ and powder‐XRD, EDX, IR, UV‐vis‐NIR, and TG‐DSC, together with the first principles calculation have been carried out to verify the structure and fully understand the structure–property relationships.

Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity

“…With the development and applications of laser science and techniques, exploiting new nonlinear optical (NLO) materials with high performance has been a topic of intensive study. Typically, the search for UV and deep‐UV NLO materials is mainly limited to borate systems [1–12] . Recently, it has become evident that introducing NLO‐active asymmetric structural units, such as π‐conjugated triangular groups, is an effective strategy to design noncentrosymmetric (NCS) materials.…”

“…Recently, it has become evident that introducing NLO‐active asymmetric structural units, such as π‐conjugated triangular groups, is an effective strategy to design noncentrosymmetric (NCS) materials. For example, similar to the BO 3 3− unit, CO 3 2− and NO 3 − anions are also π‐conjugated groups [9–17] . Many carbonates and nitrates with superior performance were designed, such as Ca 2 Na 3 (CO 3 ) 3 F, [13] RbMgCO 3 F, [14] Y 8 O(OH) 15 (CO 3 ) 3 Cl, [15] Ba 2 NO 3 (OH) 3 , [16] and RE(OH) 2 NO 3 (RE=La, Y, and Gd) [17] .…”

“…Typically,t he search forU Va nd deep-UVN LO materials is mainly limited to borate systems. [1][2][3][4][5][6][7][8][9][10][11][12] Recently,i th as become evident that introducing NLO-active asymmetric structural units, such as p-conjugated triangular groups,i sa ne ffective strategyt od esign noncentrosymmetric (NCS) materials. For example,s imilar to the BO 3 3À unit, CO 3 2À and NO 3 À anions are also p-conjugatedg roups.…”

“…For example,s imilar to the BO 3 3À unit, CO 3 2À and NO 3 À anions are also p-conjugatedg roups. [9][10][11][12][13][14][15][16][17] Many carbonates and nitrates with superiorp erformance wered esigned, such as Ca 2 Na 3 (CO 3 ) 3 F, [13] RbMgCO 3 F, [14] Y 8 O(OH) 15 (CO 3 ) 3 Cl, [15] Ba 2 NO 3 (OH) 3 , [16] and RE(OH) 2 NO 3 (RE = La, Y, and Gd). [17] Furthermore, the combinationo fN LO-active anions with distortedd 0 -or d 10 -cation-centered polyhedra or stereochemically lone-pairactive cations, generated an umber of NLO materials, of which Cs 3 Zn 6 B 9 O 21 , [18] Pb 2 (NO 3 ) 2 (H 2 O)F 2 , [19] Rb 3 VO(O 2 ) 2 CO 3 , [20] Bi 3 Te BO 9 , [21] and Pb 4 B 6 O 13 [22] are notable examples.…”

Unprecedented Formation of Potassium Borate Based Carbonate from Chloral Hydrate, Potassium Carbonate and Boric Acid

“…In addition to that borates synthesized at elevated temperatures and pressure composed of mainly tetrahedral coordination of most boron atoms are a noteworthy feature, which associate these borates to silicates. Only recently, the structural chemistry of inorganic crystals has been considerably supported by the coincorporation of more anion units such as [BO3] 3- 11 Boric acid forms complexes with organic molecules conveying adjacent hydroxyl groups through esterification reactions. While partial esterification creates monoesters (1:1 complex) retaining the planar configuration with no charge or a tetrahedral configuration with negative charge, complete esterification proceeds to the formation of a bicyclic diester (1:2 complex) structures with negatively charged tetrahedral borate anions.…”