Lone-Pair Enhanced Birefringence in an Alkaline-Earth Metal Tin(II) Phosphate BaSn2(PO4)2

The first alkaline-earth metal tin(II) phosphate, BaSn₂(PO₄)₂, has been discovered, which consists of layered structures constructed from strictly alternating [SnO₃]⁴⁻ and [PO₄]³⁻ moieties. This compound is expected to have a large birefringence with Δn≈0.071 at 1064 nm, owing to the presence of stereochemically active lone pair metal cations.     

Perfectly Encoding π-Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y,Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence

Nonlinear optical (NLO) crystal, which simultaneously exhibits strong second-harmonic-generation (SHG) response and desired optical anisotropy, is a core optical material accessible to the modern optoelectronics. Accompanied by strong SHG effect in a NLO crystal, a contradictory problem of overlarge birefringence is ignored, leading to low frequency doubling efficiency and poor beam quality. Herein, a series of rare earth cyanurates RE₅(C₃N₃O₃)(OH)₁₂ (RE=Y, Yb, Lu) were successfully characterized by 3D electron diffraction technique. Based on a “three birds with one stone” strategy, they enable the simultaneous fulfillment of strong SHG responses (2.5–4.2× KH₂PO₄), short UV cutoff (ca. 220 nm) and applicable birefringence (ca. 0.15 at 800 nm) by the introduction of rare earth coordination control of π-conjugated (C₃N₃O₃)³⁻ anions. These findings provide high-performance short-wavelength NLO materials and highlight the exploration of cyanurates as a new research area.     

An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions

Birefringent materials, which can modulate the polarization of light, are almost exclusively limited to oxides. Peroxides have long been overlooked as birefringent materials, because they are usually not stable in air. Now, the first peroxide birefringent material Rb₂VO(O₂)₂F is reported, the single crystals of which keep transparency after being exposed in the air for two weeks. Interestingly, Rb₂VO(O₂)₂F does not feature an optimal anisotropic structure, but its birefringence (Δn=0.189 at 546 nm) exceeds those of the majority of oxides. According to the first‐principles calculations, this exceptional birefringence should be attributed to the strong electronic interactions between localized π orbital of O₂^2? anions and V⁵⁺ 3d orbitals, which may be also favorable to the stability in the air for Rb₂VO(O₂)₂F. These findings distinguish peroxides as a brand‐new class of birefringent materials that may possess birefringence superior to the traditional oxides.     

Designing a deep-UV nonlinear optical monofluorophosphate

Science China Chemistry - As structural variants of famous hexagonal tungsten bronzes, hexagonal tungsten oxides (HTO) represent an important family with fascinating functional properties, such as...     

ChemInform Abstract: Synthesis,Structure, and Electronic Structure of CsAgGa2Se4.

The new title compound is prepared from a mixture of AgGaSe₂ (obtained from the elements at 900 °C, 2 d) and CsI in the molar ratio 1:2 (silica tube, Ar, 800 °C, 48 h).     

KBiMS4 (M=Si, Ge): Synthesis, structure, and electronic structure

Two new bismuth sulfides KBiSiS₄ and KBiGeS₄ have been synthesized by means of the reactive flux method. They adopt the RbBiSiS₄ structure type and crystallize in space group P2₁/c of the monoclinic system. The structure consists of (M=Si, Ge) layers separated by bicapped trigonal-prismatically coordinated K atoms. The M atom is tetrahedrally coordinated to four S atoms and the Bi atom is coordinated to a distorted monocapped trigonal prism of seven S atoms. The optical band gap of 2.25(2) eV for KBiSiS₄ was deduced from the diffuse reflectance spectrum. From a band structure calculation, the optical absorption for KBiSiS₄ originates from the layer. The Si 3p orbitals, Bi 6p orbitals, and S 3p orbitals are highly hybridized near the Fermi level. The orbitals of K have no contributions on both the upper of valence band and the bottom of conduction band.     

A7MIIRE2(B5O10)3系列紫外非线性光学晶体的研究进展

稀土硼酸盐非线性光学(NLO)材料由于其在激光技术领域的重要应用而备受关注,这主要是因为三价稀土离子如Y³⁺、Sc³⁺、Lu³⁺等可以有效抑制d-d和f-f电子跃迁从而扩宽化合物的透过范围,同时稀土原子与氧原子结合成畸变的多面体可增强材料的非线性光学效应。A₇M^IIRE₂(B₅O₁₀)₃系列(RE为稀土金属,A为碱金属、M为二价金属)化合物是稀土硼酸盐中一类重要的材料,其A、M以及RE位点具备灵活的占据方式,近年来得到了广泛关注。通过化学元素取代法,研究者们对该类化合物的种类进行拓展,目前已经合成出数十种属于该体系的化合物。这些化合物的截止边大多处在紫外甚至是波长小于200 nm的深紫外波段,非线性光学效应为0.4~2.1倍KDP,在紫外以及深紫外波段非线性光学领域中展现出了应用潜力。本文对其研究现状进行了总结,分析了其微观结构与光学性能之间的关系,并指出不同位点组分对材料非线性光学性能的影响,以期对此类化合物今后的发展提供参考。