A Series of Aluminoborates Templated or Supported by Zinc–Amine Complexes

Abstract

A series of open-framework aluminoborates (ABOs), namely, [Zn2 (en)5 ][Al2 B10 O20 ] (1), [Zn(en)(dien)][AlB5 O10 ] (2), [Zn(en)3 ][AlB7 O12 (OH)2 ] (3), [Zn(en)2 ][AlB5 O10 ] (4), K7 {AlO0.5 [BO2 (OH)]Zn@[B12 O21 (OH)3 ]}⋅H2 O (5) (en=ethylenediamine, dien=diethylenetriamine) have been made under mild solvothermal conditions and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR and UV/Vis spectroscopy, thermogravimetric analysis, and nonlinear optical determination. They were classified as two types: Compounds 1-4 contain intersecting channels and exhibit various 4-connected nets built by AlO4 tetrahedra and oxo boron clusters, zinc-amine complexes act as the templates (1-3) or directly bond to the walls of the ABO (4); compound 5 exhibits a double-layer structure made by nanosized [BO2 (OH)]Zn@[B12 O21 (OH)3 ] ({BZn@B12 }) clusters with Al2 O7 dimers, the channels are within the layer. The second harmonic generation (SHG) measurement shows that the SHG responses of 1-3 are about 2.5, 1.6, and 0.5 times that of KH2 PO4 . Compounds 1-2 are type I phase-matchable materials. UV/Vis spectroscopy indicates that compounds 1-5 are wide-band-gap semiconductors.

New Water‐Soluble Cluster Compound {Zn(en)3}3[V15Sb6O42(H2O)]⋅ (Ethylenediamine)3⋅10 H2O as a Synthon for the Generation of Two New Antimonato Polyoxovanadates

“…Zn(3) is surrounded by two en ligands (Zn−N bonds: 1.973(10)–2.018(9) Å; average: 2.003 Å) forming a distorted tetrahedron (N−Zn−N angles: 85.9(4)–128.0(4)°) (Figure ; Tables S4–S6). All angles and bond lengths are in full agreement with literature data for Zn‐containing POVs and other zinc ethylenediamine complexes …”

“…The [Zn(phen) 3 ] 2 + complexes are located between the chains, thusg enerating a layer-like arrangement that extends in all crystallographic directions ( Figure 7). [41,[43][44][45] Zn (2) is in ad istorted octahedral environment comprising four Na toms of two en ligandsa nd two Oa toms of H 2 Om olecules, with geometricp arameters in accordance with literature data (Tables S5 andS 6). The C···C distances between adjacent phen ligandsr ange from 3.588(9) to 3.918(11) (average:3 .813 , Figure S16, Ta ble S3).…”

“…(6) ), resulting in ad istorted trigonal bipyramid (Table S5). [41,[43][44][45] Zn (2) is in ad istorted octahedral environment comprising four Na toms of two en ligandsa nd two Oa toms of H 2 Om olecules, with geometricp arameters in accordance with literature data (Tables S5 andS 6). [45][46][47] The basal plane is formed by two Na nd two Oa toms, and the apical positions are occupied by two Na toms.…”

“…In the structure of {(Zn(en) 2 (H 2 O) 2 )(Zn(en) 2 )}[Zn(en) 2 V 15 Sb 6 O 42 (H 2 O)] ⋅ 8.5 H 2 O ( IV ), the three unique Zn 2+ cations are in different coordination environments. Zn(1) is surrounded by two en ligands (Zn−N bonds: 2.021(8)–2.118(9) Å; average: 2.056 Å) and one terminal O atom of the anion (Zn−O: 2.344(6) Å), resulting in a distorted trigonal bipyramid (Table S5) . Zn(2) is in a distorted octahedral environment comprising four N atoms of two en ligands and two O atoms of H 2 O molecules, with geometric parameters in accordance with literature data (Tables S5 and S6) .…”

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

“…The oxoboron polyanionic clusters are usually arranged orderly, giving rise to supermolecular assemblies via hydrogen-bond interactions. In order to construct extended structures, introducing heteroatoms as the linking centers into nonmetal borate backbones for generating extended structures has resulted in several intriguing systems, such as borophosphates, , borogermanates, − and vanadoborate. − Recently, Al atoms have been successfully introduced into the borate system, giving rise to a new family of aluminoborates (ABOs) NLO materials. ,− The tetrahedral coordination of Al 3+ ions links with the acentric polyborate clusters via covalent bonds, generating the rigid extended solid structures. Therefore, it is highly expected that ABOs can aggregate zeolitic porosity with the desirable optical behaviors of borate materials.…”