Three Alumino/Galloborate Frameworks Templated by Organic Amines: Syntheses, Structures, and Nonlinear Optical Properties

Abstract

A series of alumino/galloborates, including (H3APEA)6[Al-B5O10]9·12H2O (1, APEA = N,N′-bis­(3-aminopropyl)­ethylenedi-amine), (HDETA)2(H2DETA)2[AlB5O10]3 (2, DETA = diethylenetriamine), and (H2EDAP)­[GaB5O10]·H2O (3, EDAP = N-ethyl-diaminopropane), was solvothermally synthesized and characterized in solid-state by powder X-ray diffraction, Fourier transform infrared spectroscopy, UV–vis spectroscopy, and single-crystal X-ray diffraction. All of them feature the [MB5O10] n 2n– (M = Al or Ga) frameworks, charge-balanced by the long chain-like amine cations. Three frameworks exhibit different interlinkage modes of {MB5O10} layers, resulting in channels varying in size and shape. The flexibility of long chain-like amine cations as well as their significant structure-directing functions in forming these crystalline products is also discussed in detail. Powder second-harmonic generation measurements showed that all three compounds present a nonlinear optical property, and compound 2 exhibits type I phase-matchable optical nonlinearity.

Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties

“…The coupled [H 2 (en)] 2+ and [NH­(CH 3 ) 2 ] reside in the 14-MR channels and interact with the inorganic network via hydrogen bonds. Interestingly, the layers which contain 8- and 14-MR windows were also found in [H 2 TETA]­AlB 5 O 10 ( 3a , TETA = triethylenetetramine) and [CH 3 NH 3 ]­[CH 3 CH 2 NH 3 ]­(H 2 O) 2 [Al­(B 5 O 10 )] ( 3b ). ,, However, the layers in 3a and 3b overlap to form straight 8-, 14-MR channels, and both structures exhibit SrAl 2 (sra) topology. Besides, the structure of 3 also possess layers with 11-MR windows (the diameter of ∼9.4 × 10.4 Å 2 , Table S2, Figure S2c).…”

“…Borates have attracted much research attention from scientists in inorganic chemistry and materials chemistry owing to their significant performance in nonlinear optical (NLO) and porous materials. − Structurally, boron has the unique coordination modes of either triangular (BO 3 ) or tetrahedral (BO 4 ) geometries. They have no inversion centers and tend to polymerize into a great variety of oxoboron polyanionic units. ,− The diverse clusters increase the likelihood of creating new structures which can be functionalized for targeted applications.…”

Three Inorganic–Organic Hybrid Gallo-/Alumino-Borates with Porous-Layered Structures Containing [MB4O10(OH)] (M = Al/Ga) Cluster Units

“…The band gaps of 1 – 3 are about 4.71, 4.23, and 5.42 eV, respectively, indicating that 1 , 2 , and 3 are all wide-band-gap semiconductors. These band gaps are comparable to those of the previously reported GBOs and ABOs. ,,, …”

Transformation of the B–O Units from Corner-Sharing to Edge-Sharing Linkages in BaMBO4 (M = Ga, Al)

“…Table S6 in the Supporting Information lists 23 pairs of ABOs and GBOs; each pair of them share a common formula. Except β-SrGaBO 4 /SrAlBO 4 , SrGa 2 B 2 O 7 /SrAl 2 B 2 O 7 , , and BaGa 2 B 2 O 7 /BaAl 2 B 2 O 7 , the other 20 pairs of compounds show isomorphic structures for each pair because the cations in each pair have the same coordination numbers. As listed in Table S7 in the Supporting Information, BaAl 2 B 2 O 7 and BaGa 2 B 2 O 7 have 12- and 8-coordinated barium atoms, respectively, corresponding to ∞ 2 [BaO 6 ] 10– / ∞ 1 [Ba 2 O 10 ] 16– Ba–O configurations, [Al 2 O 7 ] 8– / ∞ 1 [Ga 2 O 6 ] 6– M–O frames, and [BO 3 ] 3– /[B 2 O 5 ] 4– B–O groups.…”