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Pb@Pb8 Basket-like-Cluster-Based Lead Tellurate-Nitrate Kleinman-Forbidden Nonlinear-Optical Crystal:
Yi-Gang Chen1, Nan Yang1, Xing-Xing Jiang2
1School of Chemistry & Material Science, Shanxi Normal University , Linfen, Shanxi 041004, China.
Abstract:
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.
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