Two layered galloborates from centric to acentric structures: syntheses and NLO properties

Abstract

Two layered galloborates (GBOs), Na3GaB4O9 (1) and Na5Ga[B7O12-(OH)]2‧2B(OH)3 (2), have been solvothermally made. 1 exhibits the unpreceeded layer built by GaO4 tetrahedra and B4O9 clusters. 2 was made by raising...

KCs2[GaB5O10](OH): A Zeolitic Galloborate Framework with a Nonlinear Optical Property

“…Up to date, most of the zeolitic borates feature 3D [AlB 5 O 10 ] n 2 n – frameworks and a small portion of them feature 3D [GeB 4 O 9 ] n 2 n – , [GaB 5 O 10 ] n 2 n – , and [GaB 4 O 9 ] n 2 n – , of which [GaB 5 O 10 ] n 2 n – frameworks are only found in M 2 [GaB 5 O 10 ]·4H 2 O (M = K, Rb) and (H 2 EDAP)­[GaB 5 O 10 ]·H 2 O (EDAP = N -ethyldiaminopropane). ,, From the synthetic point of view, the possible reason for the lack of zeolitic GBOs is that compared with Al 3+ , the larger cationic radius of Ga 3+ means it tends to link with larger oxoboron clusters or mixed oxoboron clusters for the structural stabilization. Hence, most of the reported GBOs are 2D layers, 3D pillared layers, and porous layers. − In order to make zeolitic GBOs, it is necessary to catch and obtain some metastable states in the reactions, which accord with the advantages of hydro­(solvo)­thermal syntheses. The successful solvothermal syntheses of K 2 [GaB 5 O 10 ]·4H 2 O and (H 2 EDAP)­[GaB 5 O 10 ]·H 2 O also prove our thoughts. , Up to date, most of the GBOs were made under solvothermal or solid-state conditions.…”

Cs[B3O3F2(OH)2]: discovery of a hydroxyfluorooxoborate guided by selective organic–inorganic transformation

“…Borate has been a research hotspot due to its exceptional properties, flexible structure and promising applications in optical fields. 4 c ,5 In the inorganic branch, the boron–oxygen anionic framework is generally filled with metal cations and ammonium; 6 for the organic system, a metal-free organic ligand is the additional linker. 7 In both systems, B–O groups can form a variety of structures through different connection modes.…”

“…7 In both systems, B–O groups can form a variety of structures through different connection modes. 5–9 The large electronegativity difference between B and O enables borates to have a wide transmission range. 5–9 Of course, if the anionic framework is optimally aligned to induce large polarizability anisotropy and hyperpolarizability, borates with better performance as optical materials can be expected.…”

“…5–9 The large electronegativity difference between B and O enables borates to have a wide transmission range. 5–9 Of course, if the anionic framework is optimally aligned to induce large polarizability anisotropy and hyperpolarizability, borates with better performance as optical materials can be expected. 8 d ,10 In recent years, our group has been aiming to expand the structural chemistry of the borate system, which has led to the discovery of the emergent fluorooxoborate and hydroxyfluorooxoborate branches.…”

Na1.5Cs0.5[Al{BO3}{B9O15(OH)3}1/3]: An Acentric Layered Aluminoborate with Nonlinear-Optical Properties

“…Different strategies have been applied in different synthetic systems to synthesize acentric borate crystals, which is a prerequisite of a nonlinear-optical (NLO) material. Currently, most of the explorations of borate-based NLO crystals concentrate on the alkali- and alkaline-earth-metal borates in either hydro­(solvo)­thermal or solid-state conditions, which are two mainstream synthetic methods of crystalline borate materials. − The lack of d–d and f–f electron transitions in alkali- and alkaline-earth-metal cations not only benefits the transmittance of UV and deep-UV light but also increases the possibility of acentric structures due to their spherical coordination geometries. Despite the development of the outstanding NLO borate representatives β-BaB 2 O 4 (BBO), LiB 3 O 5 (LBO), and CsLiB 6 O 10 (CLBO), − in recent years, a series of borates with excellent NLO properties have been made by different methods, such as Cs 3 Zn 6 B 9 O 21 (3.3 KDP, potassium dihydrogen phosphate), LiBa 3 (OH)­[B 9 O 16 ]­[B­(OH) 4 ] (3.1 KDP), MgB 5 O 7 F 3 (2.4 KDP), and Na 4 B 8 O 9 F 10 (0.7 KDP with a short phase-matching wavelength). ,,, …”