The first borate carbonate UV nonlinear optical material Pb7O(OH)3(CO3)3(BO3) was hydrothermally synthesized, which features a (3,9)-connected IrSi3-like structure constructed by Pb7O(OH)3(BO3) units and carbonates. This compound exhibits a large second-harmonic generation (SHG) response about 4.5 times that of KH2PO4 (KDP), attributed to synergistic interactions between the stereoeffect of the Pb(II) cations and coparallel BO3 and CO3 triangles groups.

KPb2(PO3)5shows moderate powder SHG intensities which are one half times that of KDP with a UV cut-off edge at 177 nm.

Three new mixed-alkaline borates NaMBO (M = Rb, Cs) and LiCsBO with unique structures were synthesized by the spontaneous nucleation method, and their structures were determined by single-crystal X-ray diffraction. The B-O networks of NaMBO (M = Rb, Cs) are constructed by two independent interpenetrating three-dimensional (3D) frameworks, which is the first case in anhydrous mixed-alkaline borate systems. In addition, LiCsBO shows high B-O polymerization with a new fundamental building block BO. Meanwhile, detailed structure comparisons containing the cation effect on the framework have been discussed. UV-vis-NIR diffuse reflectance spectra and the infrared spectra were measured. The band structures and the density of states were performed using density functional theory calculation.

By the application of cation substitution, five new members of cyclophosphates, RbCdPO, CsPbPO, CsSrPO, RbMgPO, and RbCaPO, were obtained by a high-temperature melt method and structurally analyzed. The five compounds have identical stoichiometries, and all of them feature a three-dimensional network, which consists of MO (M = Cd, Mg, Ca, Pb, Sr) octahedra and cyclic PO units, while alkali-metal atoms are located within the network. However, RbCdPO and CsPbPO belong to the asymmetric space groups P6̅ c2 and Pna2, respectively, and the other three compounds belong to orthorhombic space group Pnma. Detailed structure comparisons in the M-M-P-O and (MMPO) ( n = 1, 2, 6) systems are discussed. Remarkably, KMgPO as one of the cyclophosphate members exhibits a second harmonic generation (SHG) intensity about 0.2 times that of KHPO (KDP), RbCdPO, and CsPbPO also show SHG responses 0.1 times that of KDP. In addition, the related optical properties are discussed. Furthermore, theoretical calculations and dipole moments were calculated to explain the relation of structure and optical properties.

LiGeBO4 is found to be a material that can balance a large band gap (>6.2 eV) and strong SHG coefficient (2 × KDP), which is rarely seen in tetrahedral-based crystals.

A new metal polyphosphate, α-CsBa(PO), exhibiting the first example of a linear P-O-P bond angle in a one-dimensional (PO) chain has been reported. Interestingly, α → β phase transition occurs in CsBa(PO) along with the P-O-P bonds varying from linear to λ-shape, suggesting that α-CsBa(PO) with unfavorable linear P-O-P bonds is more stable at ambient temperature.

The ternary thiophosphate PbPS3 was synthesized by high temperature solid-state reaction using PbS, P and S. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in P21/c space group. It...

The nonlinear-optical (NLO) materials with second-harmonic-generation (SHG) response need to crystallize in the noncentrosymmetric space group. It is very difficult to control the synthetic conditions to solely form a noncentrosymmetric phase for the materials with noncentrosymmetric and centrosymmetric conformations. Herein, we found that the temperature and halogen anion play an important role during the formation procedure of the pure noncentrosymmetric or centrosymmetric phase for the halogen-based family of coordination polymers to yield hybrid materials with a phase-matching SHG response as well as inherit the primary excellent photonic property of organic linkers. Our results provide a good choice for the design and construction of novel materials with a particular photonic property.