Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties
Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties
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DOI：
10.1021/acs.inorgchem.2c04084
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发表时间：
2023-01-23
影响因子：
4.6
通讯作者：
Yang, Guo-Yu
中科院分区：
文献类型：
--
作者：
Li, Xu-Yan;Li, Jin-Hua;Yang, Guo-Yu
用溶剂热法合成了两种无中心的硼铝酸盐[Zn（en）2Al{B5 O 9（OH）}{BO（OH）2}]（1）和[Cd（en）2AlB 5 O 10]中心点H2O（2）（en =乙二胺）。1包括使用B5 O 9（OH）簇和AlO 3 {BO（OH）2}基团的二维（2D）波状ABO层，其中两个单元可以被视为三连接节点，并且将ABO层简化为hcb型网络。2的特征在于具有由严格交替连接的B5 O 10簇和AlO 4单元构成的独特的unc-type网络的偏心三维（3D）多孔框架。通过在相同的溶剂体系中调整合成条件，消除层1中的末端羟基，实现了从2D层1到3D骨架2的结构转变。金属-胺配合物Zn（en）2/Cd（en）2分别与无机壁结合并位于骨架1和2的空腔中。化合物1和2表现出大的二次谐波产生（SHG）的响应，分别是2.2和2.7倍的KH 2 PO 4（KDP），这是最大的粉末SHG响应所有深紫外（深UV）ABO。1和2的UV-vis漫反射光谱在190 nm以下显示出宽的透明窗口。密度泛函理论（DFT）计算表明，B-O单元和引入的扭曲d10金属多面体的光学性质起着决定性的作用，这两个化合物。
Two acentric aluminoborates (ABOs), [Zn(en)2Al{B5O9(OH)}{BO(OH)2}] (1) and [Cd(en)2AlB5O10]center dot H2O (2) (en = ethylenediamine), have been solvothermally made. 1 includes a two-dimensional (2D) wavy ABO layer using B5O9(OH) clusters and AlO3{BO(OH)2} groups, in which both units can be regarded as three-connected nodes, and simplifying the ABO layer to a hcb-type network. 2 features an acentric three-dimensional (3D) porous framework with a unique unc-type network constituted by strictly alternating connected B5O10 clusters and AlO4 units. The structural transformation from a 2D layer 1 to a 3D framework 2 was achieved with the elimination of the terminal hydroxyls in layer 1 by adjusting synthetic conditions in the same solvent system. Metal-amine complexes Zn(en)2/Cd(en)2 bond to the inorganic walls and are located in the cavity of frameworks 1 and 2, respectively. Compounds 1 and 2 exhibit large second-harmonic generation (SHG) responses that are 2.2 and 2.7 times those of KH2PO4 (KDP), respectively, which are among the largest powder SHG responses for all deep-ultraviolet (deep-UV) ABOs. The UV-vis diffuse reflectance spectra of 1 and 2 show a wide transparency window below 190 nm. Density functional theory (DFT) calculations indicate that the B-O units and the introduced distorted d10 metal polyhedra played a decisive role in the optical properties of both compounds.