5 years ago

Extending Unique 1D Borate Chains to 3D Frameworks by Introducing Metallic Nodes

Extending Unique 1D Borate Chains to 3D Frameworks by Introducing Metallic Nodes
Shi-Jia Sun, Jie Zhang, Qi Wei, Guo-Yu Yang
Two novel alkali/alkaline-earth borates, Ba6[B6O9(OH)6]2(H3BO3) (1) and Li7MAlB12O24 (M=Ba, Sr, Ca) (2 a–c), with 1D and 3D structures have been made hydrothermally and characterized. 1 features a rare 1D anionic chain built by hexaborate clusters of B6O11(OH)6; each made of six BO4/BO2(OH)2 tetrahedra. The anionic chains are embedded in the channels of a Ba6-based wheel-cluster open-framework. On the basis of the structural analyses of 1, by incorporating Al atoms as the linkers and tuning the reaction conditions, the novel anhydrous 3D aluminoborates (ABOs) 2 a–c have been successfully obtained, constructed from B6O14-based cluster chains and AlO6 octahedra. The 3D ABO framework and 3D Ba-O-Li network are interpenetrated to give a final dense structure. The study not only realized the expansion of the structure from the 1D chain of 1 to the 3D dense ABOs 2 a–c, but also obtained the first 3D AlO6-containing ABOs made under hydrothermal conditions. Different from the previously known 4-connected zeolite-type ABOs, alternately arranged from AlO4 tetrahedra and oxo-boron clusters, the AlO6 octahedra in 2 a–c as the linkers join to six 1D B6O14-based cluster chains to produce 3D ABOs. The optical diffuse reflectance spectra reveal that 2 a–c have wide range transparency. In addition, the thermal property analysis proves that 2 a–c are congruently melting compounds and possess high thermostability. Two types of borates with novel structures have been hydrothermally made and characterized. 1 features a rare 1D B−O chain built by a unique [B6O11(OH)6] cluster. On the basis of the structural analyses of 1, through introducing aluminium atoms as the heteroatoms, the expansion of structures was achieved, from 1D chain to 3D anhydrous dense aluminoborates with high thermostability, showing the first 3D hydrothermally synthesized ABOs made of AlO6 octahedra and B−O chains.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701222

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