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

Abstract

The first lead tellurate-nitrate nonlinear-optical (NLO) crystal, PbTeO(OH)(NO), featuring a 3D anionic diamondlike toplogical structural motif formulated as [PbO] constructed by unique nonanuclear basket-shaped Pb@PbO clusters has been hydrothermally achieved, in which the Pb@PbO cluster shows a core-shell structure with one PbO polyhedron enclosed by eight PbO (x = 3 and 4) polyhedera via edge and face sharing. The hexavalent Te in TeO(OH) octahedra is linked to a [PbO] cluster to form a rare [PbTeO(OH)] cationic framework. The compound demonstrates a powder second-harmonic-generation (SHG) response of about 1.2 times that of KHPO (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.

Surface Transformations of Lead Oxides and Carbonates Using First-Principles and Thermodynamics Calculations

“…For example, Pb 2+ can form a variety of noncentrosymmetric materials with oxygen-containing ligands. Well-known examples that find use as nonlinear optical devices display a diverse range of compositions such as Pb 16 (OH) 16 (NO 3 ) 16 , Pb 9 Te 2 O 13 (OH)­(NO 3 ) 3 , Pb 3 SeO 5 , and (Pb 4 O)­Pb 2 B 6 O 14 . − Beyond oxide-based ligands, Pb 2+ halides are finding increased usage as a starting material in the synthesis of newly developed two-dimensional (2D) hybrid perovskites with tunable optical properties. Example materials include (CH 3 NH 3 )­PbI 3 , (BZA) 2 PbBr 4– x Cl x , and (CH 3 ) 3 SPbI 3 , − where the combination of a lone electron pair on Pb 2+ and a variety of organic ligands can result in multiple steric configurations.…”

Hydrogen-Bond-Assisted Alignment of [MCu(SeO3)4Cl(H2O)]4– (M = Fe, Ga) Anionic Layers to Form Two Polar Oxychlorides: Pb2MCu(SeO3)4Cl(H2O)

“…Recently, Lin et al summarized a general and effective route aiming at exploration of infrared nonlinear optical crystals with a chemical substitution method in known structures. − Another strategy used to assemble noncentrosymmetric structures is through cooperative combination of different asymmetric units. Several asymmetric units that can be commonly utilized include π-conjugated systems (borates, carbonates, and nitrates), − electron lone-paired metal oxide polyhedron (such as Pb 2+ , Se 4+ , and I 5+ ), cations with distorted tetrahedron or octahedron coordination with d 10 electrons (such as Zn 2+ and Ge 4+ ), and d 0 transition-metal cations with second-order Jahn–Teller (SOJT) distortion (such as Ti 4+ and Mo 6+ ). When these asymmetric units are aligned along certain directions, the local dipole moments will enhance with each other constructively and hence crystallize in a noncentrosymmetric space group with a polar structure.…”

Experiment and First-Principles Calculations of A2Mg2TeB2O10 (A = Pb, Ba): Influences of the Cosubstitution on the Structure Transformation and Optical Properties

“…), one-dimensional (1D) chains, 2D layers, and 3D frameworks. − Moreover, borates have significant advantages for function materials, such as large band gap, low sintering temperature, low cost, and large laser-damaged threshold. Like borates, tellurites and tellurates also have rich structures and have received much attention for their important applications as ferroelectric, magnetic, and thermoelectric materials. − To obtain materials with a rich structure chemistry and excellent properties, the B–O groups and Te–O groups are combined in one structure, which results in the formation of a new class of compounds, telluro-borates.…”