New Entangled Coordination Networks Based on Charge‐Tunable Keggin‐Type Polyoxometalates |
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| Authors: | Xiu‐Li Hao Yuan‐Yuan Ma Dr Yong‐Hui Wang Long‐Yang Xu Dr Fu‐Chen Liu Mao‐Mao Zhang Prof Yang‐Guang Li |
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| Affiliation: | 1. Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024 (P.R. China);2. School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, 300384 (P. R. China) |
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| Abstract: | Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, CoII(HBBTZ)(BBTZ)2.5]PMo12O40] ( 1 ), CuI(BBTZ)]5BW12O40] ? H2O ( 2 ), CuII(BBTZ)]3AsWV3WVI9O40] ? 10 H2O ( 3 ), and CuII5(BBTZ)7(H2O)6]P2W22Cu2O77(OH)2] ? 6 H2O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo12O40}>{XW12O40}>{XW12?nTMnO40}. |
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| Keywords: | entangled coordination networks Keggin‐type photochemistry polyoxometalates |
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