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Synthesis and photo-/electro-catalytic properties of Keggin polyoxometalate inorganic-organic hybrid layers based on d10 metal and rigid benzo-diazole/-triazole ligands

Abstract

Five Keggin polyanion-templated inorganic-organic hybrid, (H3biz)4[SiMo12O40] (1), (H3biz)3(H2biz)[PMo12O40] (2), [{Cu7(Hbtz)2(btz)4}{PMo12O40}] (3), [{Ag7(Hbtz)2(btz)4}{AsW12O40}] (4), and [{Ag9(H2biz)2(biz)4} {H2PW12O40}] (5) (H2biz = benzimidazole, Hbtz = benzotriazole) have been hydrothermally synthesized and characterized by elemental analysis, thermogravimetry (TG), infrared spectroscopy(IR), ultraviolet spectoscopy (UV), and single-crystal X-ray diffraction. A remarkable aspect of compound 1 is that six pairs of H2biz ligands circlely arranged around {SiMo12} cluster, leading to the formation of a unique 2-D supramolecular layer. The most prominent structure of compound 2 is that protonated Hbiz ligands link {PMo12} cluster into hexagon units, which are further extended into 2-D supramolecular array via the edge-sharing modes. The Keggin {PMo12} and {AsW12} clusters in compound 3 and 4 are firstly extended into octa-connected 2-D sheets by unusual heptanuclear complex {M7(Hbtz)2(btz)4} (M = Cu for 3; Ag for 4) linker. Interestingly, there exist two kinds of M-M interactions in the heptanuclear units. Compound 5 exhibits unprecedented 2D network constructed from nine-nuclear silver complex {Ag9(biz)4(H3biz)2} bridge and {PW12} cluster. Most strikingly, carbene silver and coexistence of multiple Ag-C bonds are firstly observed in the nine-nuclear unit. Intensive CuI/AgI–π interactions and π–π stacking act important roles in the packing arrangements of 3-5. Additionally, electrochemical, electrocatalytic, fluorescent, and photocatalytic properties of 1-5 have been investigated in detail.

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Publication details

The article was received on 18 Jul 2017, accepted on 11 Sep 2017 and first published on 12 Sep 2017


Article type: Paper
DOI: 10.1039/C7NJ02615C
Citation: New J. Chem., 2017, Accepted Manuscript
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    Synthesis and photo-/electro-catalytic properties of Keggin polyoxometalate inorganic-organic hybrid layers based on d10 metal and rigid benzo-diazole/-triazole ligands

    Y. Cao, J. Lv, K. Yu, C. Wang, Z. Su, L. Wang and B. Zhou, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ02615C

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