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Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
pH-dependent assembly of two polyoxometalate host-guest structural isomers based on Keggin polyoxoanion templates
Lei Zhang1, Wenbin Yang, Xiaofei Kuang
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China. czlu@fjirsm.ac.cn.
Abstract:
Two interesting polyoxometalate-templated host–guest compounds 1 and 2 with the same chemical formulae of [Ag6(tpt)4(SiW12O40)Cl2]·2H2O have been obtained by hydrothermal reactions of monolacunary Keggin-type K8[α-SiW11O39]·13H2O with CH3COOAg and tpt ligands under different pH conditions. Compounds 1 and 2 are structural isomers. In 1, the novel chair-like tetranuclear [Ag4(μ3-Cl)2]2+ clusters and additional Ag+ ions are linked by tpt ligands to form a 2D double-layered structure featured with two different types of voids in the layer, and the double-layers are stacked into a 3D host supramolecular framework with 1D channels filled with Keggin [SiW12O40]4− polyoxoanions and water molecules as guests. In 2, Ag+ ions are linked by tpt ligands into a 3D framework of 10(3)-ths topology. The most outstanding structural feature of 2 is that upon six-fold interpenetration among 10(3)-ths nets there are still nanosized channels along the a axis to accommodate Keggin polyoxoanions and water molecules as guests. Compound 2 represents the first example of six-fold interpenetrating cationic networks templated with polyoxoanions. In this work, the obvious differences in structure between 1 and 2 show that hydrochloric acid solution conditions, which offer not only H+ to regulate the pH value but also Cl− to coordinate with Ag+ ions, play an important role in the formation of host frameworks templated by Keggin-type polyoxoanions. The photoluminescence properties of 1 and 2 have been investigated in the solid state.
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