US EPA

4122906 

Journal Article 

Pb@Pb8 Basket-like-Cluster-Based Lead Tellurate-Nitrate Kleinman-Forbidden Nonlinear-Optical Crystal: Pb9Te2O13(OH)(NO3)3 

Chen, YG; Yang, N; Jiang, XX; Guo, Y; Zhang, XM 

2017 

Yes 

Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 

AMER CHEMICAL SOC 

WASHINGTON 

56 

14 

7900-7906 

English 

28649843 

10.1021/acs.inorgchem.7b00647 

WOS:000405972200035 

The first lead tellurate-nitrate nonlinear-optical (NLO) crystal, Pb9Te2O13(OH)(NO3)3, featuring a 3D anionic diamondlike toplogical structural motif formulated as [Pb9O13](8-) constructed by unique nonanuclear basket-shaped Pb@Pb8O14 clusters has been hydrothermally achieved, in which the Pb@Pb8O14 cluster shows a core-shell structure with one PbO10 polyhedron enclosed by eight PbOx (x = 3 and 4) polyhedera via edge and face sharing. The hexavalent Te in TeO5(OH) octahedra is linked to a [Pb9O13](8-) cluster to form a rare [Pb9Te2O13(OH)](3+) cationic framework. The compound demonstrates a powder second-harmonic-generation (SHG) response of about 1.2 times that of KH2PO4 (KDP) as well as a wide transparency range. Calculations on the local dipole moment and SHG coefficient reveal that the net polarization is zero because of a Kleinman-forbidden point group. Further analysis shows that the SHG response results from structure-induced variations by thermal vibrations of the lattice rather than the intrinsic dipole moment, which offers another insight on the design of new NLO materials.