A Hydrogen Bonded Supramolecular Framework Birefringent Crystal

Birefringent crystals could modulate the polarization of light and are widely used as polarizers, waveplates, optical isolators, etc. To date, commercial birefringent crystals have been exclusively limited to purely inorganic compounds such as α-BaB₂O₄ with birefringence of about 0.12. Herein, we report a new hydrogen bonded supramolecular framework, namely, Cd(H₂C₆N₇O₃)₂⋅8 H₂O, which exhibits exceptionally large birefringence up to about 0.60. To the best of our knowledge, the birefringence of Cd(H₂C₆N₇O₃)₂⋅8 H₂O is significantly larger than those of all commercial birefringent crystals and is the largest among hydrogen bonded supramolecular framework crystals. First-principles calculations and structural analyses reveal that the exceptional birefringence is mainly ascribed to strong covalent interactions within (H₂C₆N₇O₃)⁻ organic ligands and the perfect coplanarity between them. Given the rich structural diversity and tunability, hydrogen bonded supramolecular frameworks would offer unprecedented opportunities beyond the traditional purely inorganic oxides for birefringent crystals.     

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...     

Alloying n‐Butylamine into CsPbBr3 To Give a Two‐Dimensional Bilayered Perovskite Ferroelectric Material

Cesium‐lead halide perovskites (e.g. CsPbBr₃) have gained attention because of their rich physical properties, but their bulk ferroelectricity remains unexplored. Herein, by alloying flexible organic cations into the cubic CsPbBr₃, we design the first cesium‐based two‐dimensional (2D) perovskite ferroelectric material with both inorganic alkali metal and organic cations, (C₄H₉NH₃)₂CsPb₂Br₇ ( 1 ). Strikingly, 1 shows a high Curie temperature (T_c=412 K) above that of BaTiO₃ (ca. 393 K) and notable spontaneous polarization (ca. 4.2 μC cm^?2), triggered by not only the ordering of organic cations but also atomic displacement of inorganic Cs⁺ ions. To our knowledge, such a 2D bilayered Cs⁺‐based metal–halide perovskite ferroelectric material with inorganic and organic cations is unprecedented. 1 also shows photoelectric semiconducting behavior with large “on/off” ratios of photoconductivity (>10³).     

A Photoferroelectric Perovskite‐Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects

Perovskite‐type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite‐type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead ( 1 ), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner‐sharing PbBr₆ octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10⁴), which compete with the most active photovoltaic material CH₃NH₃PbI₃. In 1 the temperature‐dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices.     

A new synthetic pathway of segmented tri-block copolyether

A new synthetic pathway of A–B–A tri-block copolyether which is composed of a hydrophilic poly(oxyethylene) unit as an A part and a hydrophobic poly(oxy-2-methyl-trimethylene) unit as a B part is proposed. Telechelic α-tosyl-ω-tosyloxypoly(oxy-2-methyl-trimethylene) derived from tosylation of poly(oxy-2-methyl-trimethylene glycol) (PMTG) was allowed to react with poly(ethylene glycol) (PEG) in the presence of sodium hydroxide. T_g of the resulting A–B–A tri-block copolyether (PEMG) (M?_n = 1600) was ?72°C and its specific gravity [D₄¹⁵] was 1.055.     

Ba3Y2B6O15, a novel cubic borate

Single crystals of tribarium diyttrium hexaborate, which crystallized in the cubic system, have been obtained by spontaneous crystallization from a high‐temperature melt using Li₂O–BaO–B₂O₃ as flux. Its structure is composed of isolated [B₂O₅]⁴⁻ groups, irregular BaO₉ polyhedra and regular YO₆ polyhedra which occupy alternate sites running along the [111] direction. Irregular BaO₉ polyhedra and regular YO₆ polyhedra construct a three‐dimensional framework, which is reinforced by [B₂O₅]⁴⁻ groups.     

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 O₂²⁻ 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.     

A High-Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π-Delocalization

Common nonlinear optical (NLO) crystals consist of traditional functional building blocks with inherent optical limitation. Herein, inspired by traditional (B₃O₆)³⁻ inorganic building block, we theoretically identified a new type of organic functional building blocks and then successfully synthesized the first cyamelurate NLO crystal, Ba(H₂C₆N₇O₃)₂ ⋅ 8 H₂O. To our surprise, the constituent (H₂C₆N₇O₃)⁻ building block is not in structurally optimal arrangement, but Ba(H₂C₆N₇O₃)₂ ⋅ 8 H₂O exhibits excellent optical properties including wide band gap of 4.10 eV, very large birefringence of 0.24@550 nm, and exceptionally strong second-harmonic generation (SHG) response of about 12×KH₂PO₄. Both the SHG response and birefringence are much larger than those of commercial NLO crystal β-BaB₂O₄ with optimally aligned (B₃O₆)³⁻ building block. Theoretical calculations suggest that the expanded π-conjugation delocalization within (H₂C₆N₇O₃)⁻ vs (B₃O₆)³⁻ should be responsible to the enhanced performance. This work implies that there is still much room to develop new NLO crystals with excellent functional building blocks that may be longly neglected.     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.