Lead Tellurite Crystals BaPbTe₂O₆ and PbVTeO₅F with Large Nonlinear-/Linear-Optical Responses due to Active Lone Pairs and Distorted Octahedra

The exploration of nonlinear-/linear-optical crystal materials with high performance is an extremely difficult research project. Herein, the two new lead tellurite crystals BaPbTe₂O₆ and PbVTeO₅F were successfully obtained through a facile hydrothermal synthesis strategy. BaPbTe₂O₆ lies in the noncentrosymmetric (NCS) and chiral orthorhombic space group P2₁2₁2₁, featuring a unique _∞¹[PbTe₂O₆] chain consisting of the PbO₄ and TeO₃ building units, while PbVTeO₅F belonging to the centrosymmetric (CS) orthorhombic space group Pbca manifests a 2D layer made up of _∞¹[PbO₄F₂] chains and novel [V₂Te₂O₁₀F₂] clusters. Further, a systematic analysis of lead tellurites finds that the coordination geometries of the Pb atom exert a considerable influence on the connection modes of Pb–O and Te–O building units. BaPbTe₂O₆ shows a great second-harmonic-generation (SHG) effect of ∼5× the benchmark KH₂PO₄ (KDP) and a large optical birefringence of 0.086 at 590 ± 3 nm. PbVTeO₅F demonstrates a remarkably larger birefringence of 0.142 at 590 ± 3 nm, benefiting from the introduction of the VO₅F octahedral unit. Theoretical studies reveal that the large SHG and birefringence in BaPbTe₂O₆ can be attributed to TeO₃ and PbO₄ polyhedra with active lone pairs, while the remarkably enlarged birefringence in PbVTeO₅F is attributable to the highly distorted octahedral VO₅F. The functional orientations of active building units may offer a practical insight into the design of the desired optical functional materials.