Chain-like [Sx] (x=2–6) Units Realizing Giant Birefringence with Transparency in the Near-Infrared for Optoelectronic Materials

Birefringent crystals are requisite optical devices in laser and modern opto-electronic fields. Development of excellent birefringent materials is still challenging. Herein, the linear or chain-like [S_x] (x=2–6) species were theoretically proved to be the origin of the large birefringence, and could be regarded as birefringent genes. Besides, the metal polysulfide family was first proposed to be rich birefringent materials source, among which Cs₂S₆ realizes giant birefringence 0.58@1064 nm together with a wide band gap of 1.70 eV (based on the generalized gradient approximation). Moreover, the first dual-anion group polysulfide Na₄Ba₃(S₂)₄S₃ was obtained, showing wide infrared transmission range (0.5–6.2 μm), wide band gap (2.3 eV), and large birefringence (0.37 at 1064 nm). This work provides a new guiding thought for exploring large birefringence crystals in the future.     

A Paramagnetic Compass Based on Lanthanide Metal-Organic Framework

Macroscopic compass-like magnetic alignment at low magnetic fields is natural for ferromagnetic materials but is seldomly observed in paramagnetic materials. Herein, we report a “paramagnetic compass” that magnetically aligns under ∼mT fields based on the single-crystalline framework constructed by lanthanide ions and organic ligands (Ln-MOF). The magnetic alignment is attributed to the Ln-MOF's strong macroscopic anisotropy, where the highly-ordered structure allows the Ln-ions’ molecular anisotropy to be summed according to the crystal symmetry. In tetragonal Ln-MOFs, the alignment is either parallel or perpendicular to the field depending on the easiest axis of the molecular anisotropy. Reversible switching between the two alignments is realized upon the removal and re-adsorption of solvent molecules filled in the framework. When the crystal symmetry is lowered in monoclinic Ln-MOFs, the alignments become even inclined (47°-66°) to the field. These fascinating properties of Ln-MOFs would encourage further explorations of framework materials containing paramagnetic centers.     

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

The combination of Sn^II or Sb^III 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 Sn^II or Sb^III 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 Sn^II, Sb^III-based birefringent crystals with birefringence investigated are summarized, including their crystal structure and optical properties, especially birefringence. This review also presents the influence of Sn^II, Sb^III with stereochemically active lone pair on the optical anisotropy. We hope that this work provides a clear perspective on the crystal chemistry of Sn^II, Sb^III-based optical functional crystals and promotes the development of new birefringent crystals with large optical anisotropy.