Ion-Exchangeable Microporous Polyoxometalate Compounds with Off-Center Dopants Exhibiting Unconventional Luminescence
Dan-Dan Zhou+,[a] ,Qing Zhao+,[b], Fu-Ping Zhu+,[c] ,Zhi-Gang Zhang[b], Yang Zhou[a],Zi-Jun Yong[a], Ju-Ping Ma[a], Yoshihiro Kuroiwa[b], Chikako Moriyoshi[b], Yong-Zheng Fang[c],Jia-Li Gu[d], Jie Shu[d], Zhi-Yong Li[a], Jian-Mei Chen[e], Li-Rong Zheng[f], and Hong-Tao Sun*[a]（孙洪涛）
[a] College of Chemistry, Chemical Engineering,and Materials Science, Soochow University, Suzhou 215123 (P.R. China)
[b] Department of Physical Science Hiroshima University, Higashihiroshima, Hiroshima 739-8526 (Japan)
[c] School of Materials Science and Engineering,Shanghai Institute of Technology, Shanghai 201418 (P.R. China)
[d] Analysis and Testing Center,Soochow University, Suzhou 215123 (P.R. China)
[e] Institute of Functional Nano & Soft Materials (FUNSOM) ,Collaborative Innovation Center of Suzhou Nano Science and Technology,Soochow University, Suzhou 215123 (P.R. China)
[f] Beijing Synchrotron Radiation Facility, Institute of High Energy Physics ,Chinese Academy of Sciences, Beijing 100049 (P.R. China)
[+] These authors contributed equally to this work.
Chem. Eur. J.2018, 24, 9976--9982
The synthesis of luminescent polyoxometalates (POMs) typically relies on the assembly of POM ligands with rare earth or transition metals, placing significant constraints on the composition, structure, and hence the luminescence properties of the resultant systems. Herein, we show that the ion-exchange strategy can be used for the synthesis of novel POM-based luminescent materials. We demonstrate that introducing bismuth ions into an ion-exchangeable, microporous POM compound yields an unconventional system luminescing in the near-infrared region. Experimental characterization, coupled with quantum chemical calculations, confirms that bismuth ions site-specifically occupy an off-center site in the lattice, and have an asymmetric coordination geometry unattainable by other means, thus giving rise to peculiar emission. Our findings offer an effective strategy for the synthesis of POM-based luminescent materials, and the design concept may potentially be adapted to the creation of POM-based systems with other functionalities.
链接：https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.201801829