Liu Yuan, Pan Rui, Cheng Jian-Wen, He Huan, Yang Bai-Feng, Zhang Qiang, Yang Guo-Yu
MOE Key Laboratory of Cluster Science, School of Chemistry, Beijing Institute of Technology, Beijing 100081 (China), Fax: (+86) 10-6891-8572.
Key Laboratory of the Ministry of Education for Advanced Catalysis, Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004 (China).
Chemistry. 2015 Oct 26;21(44):15732-9. doi: 10.1002/chem.201501420. Epub 2015 Sep 4.
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.
一系列开放框架的铝硼酸盐（ABO），即[Zn₂(en)₅][Al₂B₁₀O₂₀]（1）、[Zn(en)(dien)][AlB₅O₁₀]（2）、[Zn(en)₃][AlB₇O₁₂(OH)₂]（3）、[Zn(en)₂][AlB₅O₁₀]（4）、K₇{AlO₀.₅[BO₂(OH)]Zn@[B₁₂O₂₁(OH)₃]}⋅H₂O（5）（en = 乙二胺，dien = 二乙三胺）已在温和的溶剂热条件下合成，并通过单晶X射线衍射、粉末X射线衍射、元素分析、红外和紫外/可见光谱、热重分析以及非线性光学测定进行了表征。它们被分为两类：化合物1 - 4包含交叉通道，并呈现出由AlO₄四面体和氧硼簇构建的各种4连接网络，锌 - 胺配合物充当模板（1 - 3）或直接与ABO的壁键合（4）；化合物5呈现出由纳米尺寸的[BO₂(OH)]Zn@[B₁₂O₂₁(OH)₃]（{BZn@B₁₂}）簇与Al₂O₇二聚体构成的双层结构，通道在层内。二次谐波产生（SHG）测量表明，1 - 3的SHG响应分别约为KH₂PO₄的2.5、1.6和0.5倍。化合物1 - 2是I型相位匹配材料。紫外/可见光谱表明化合物1 - 5是宽带隙半导体。
