Design, synthesis and excellent third-order NLO properties of two new polyoxometalates constructed from Keggin polyanions bonded by a solvent molecule

Hao Miao; Yayu Dong; Ziwang Chen; Xingxiang He; Gonghao Hu; Yan Xu

doi:10.1039/c6dt02320g

Design, synthesis and excellent third-order NLO properties of two new polyoxometalates constructed from Keggin polyanions bonded by a solvent molecule

Dalton Trans. 2016 Aug 9;45(32):12717-22. doi: 10.1039/c6dt02320g.

Authors

Hao Miao¹, Yayu Dong², Ziwang Chen², Xingxiang He², Gonghao Hu², Yan Xu¹

Affiliations

¹ College of Chemistry and Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, PR China. yanxu@njtech.edu.cn and Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, PR China.
² College of Chemistry and Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, PR China. yanxu@njtech.edu.cn.

PMID: 27453327
DOI: 10.1039/c6dt02320g

Abstract

Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)](5-), while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively.