Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin-based Ternary Halides.

It is important to establish and clarify the relationship between stereochemically active lone pairs and birefringence, since it is one of the significantly effective routes to explore birefringent crystals by introducing Sn-centered polyhedra with stereochemically active lone pairs. Herein, four tin(II)-based ternary halides A3 SnCl5 and ASn2 Cl5 (A=NH4 and Rb) have been synthesized successfully. The experimental birefringence of Rb3 SnCl5 and RbSn2 Cl5 is larger than or equal to 0.046 and 0.123@546 nm, respectively. Through investigating the alkali or alkaline-earth metal tin(II)-based ternary halides, the structure-performance relationship has been concluded between stereochemically active lone pairs and optical anisotropy. It is beneficial to the analysis and prediction of birefringence in tin-based halides and provides a guide for exploring tin(II)-based optoelectronic functional materials.

Recent Development of SnII , SbIII -based Birefringent Material: Crystal Chemistry and Investigation of Birefringence.

The combination of SnII or SbIII with π, non-π-conjugated units has produced birefringent crystals with birefringence ranging from 0.005 to 0.468@1064 nm. It is proven that introducing SnII or SbIII into crystals is a feasible strategy to enlarge the birefringence, which not only promotes the miniaturization of fabricated devices, but also effectively modulates polarized light. Herein, recently discovered SnII , SbIII -based birefringent crystals with birefringence investigated are summarized, including their crystal structure and optical properties, especially birefringence. This review also presents the influence of SnII , SbIII with stereochemically active lone pair on the optical anisotropy. We hope that this work provides a clear perspective on the crystal chemistry of SnII , SbIII -based optical functional crystals and promotes the development of new birefringent crystals with large optical anisotropy.

Sn2 PO4 I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π-Conjugated Phosphate.

Exploring non π-conjugated phosphate birefringent crystal with a large birefringence has been a great challenge. Herein, based on the unique two-dimensional layered structure in KBe2 BO3 F2 (KBBF), two new compounds, Sn2 PO4 I and Sn2 BO3 I, were designed and synthesized successfully, maintaining the layer structural feature and enhancing the optical anisotropy of crystals. In particular, the birefringence of Sn2 PO4 I is larger than or equal to 0.664 @546 nm, which is largest among the reported borates and phosphates, even surpassing commercial birefringent crystals YVO4 and TiO2 . This work indicates that a breakthrough in birefringence of inorganic compound was achieved. Also, it provides a guiding idea for exploring large birefringence materials in the future.

An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses.

Antimony(III) borates with a stereochemical active lone pair remained unknown, although the first antimony borate was reported more than twenty years ago. Now, the first antimony(III) borate in a closed system is successfully synthesized, namely SbB3 O6 . Remarkably, SbB3 O6 not only exhibits an exceptional linear optical response, that is, birefringence of Δn=0.290 at the wavelength of 546 nm, which is the largest among borates, but also has a strong nonlinear optical response of 3.5 times larger than the benchmark KH2 PO4 , exceeding those of most borates. Theoretical calculations reveal that the coexistence of strong linear and nonlinear optical responses in SbB3 O6 should be attributable to the synergistic effect of π-conjugated B-O anionic groups and Sb3+ with stereochemically active lone pair. This work provides a new class of optical bi-functional materials with potential prospects in integrated optical devices.