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Updated: Nov 3, 2025
Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Exploring the Coordination Modes of a Keggin-Type [ZnW12O40]6- Anionic Cluster: Bonding Patterns, Crystal Structure,
Ke-Ke Guo1, Ming Xu1, Yue Zheng1
1Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, People's Republic of China.
Abstract:
Polyoxometalate-based organic-inorganic hybrid compounds (POIHCs) have been greatly developed due to their wide application prospects, but the pursuit of their directed synthesis via molecular design still remains a challenge. Herein, we demonstrate that the coordination modes of the Keggin-type [ZnW12O40]6- anion can be tuned, which leads to different semiconductor characteristics. Using the same building block, ligand, and metal ion (ZnW12, phen, Cu2+), we synthesized three new POIHCs with different bonding patterns by means of different coordination modes of ZnW12. The three POIHCs (H2phen){ZnW12O40[Cu(phen)2]2}·3H2O (1), {ZnW12O40[Cu(phen)(H2O)2]2[Cu(phen)(H2O)]}·3H2O (2), and (Me4N)2{ZnW12O40[Cu(phen)(H2O)]2}·5H2O (3) (phen = 1,10-phenanthroline) have been structurally characterized by single-crystal X-ray diffraction. Compound 1 appears as a zero-dimensional coordination complex cluster, while compounds 2 and 3 are both 1D chain structures with different Cu2+ bridge linkages. Although these three POIHCs possess the same chemical components, their semiconductor properties are different, which is demonstrated by measurements of transient photocurrent and band gap (Eg) values. Furthermore, we carried out comparative experiments on the photoconductivity performance of compounds 1-3 and their photocatalytic reduction from O2 to H2O2, indicating the significant influence of the energy level matching on the photocatalytic activity.
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