Ce3F4(SO4)4: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Wu, Tianhui; Jiang, Xingxing; Wu, Chao; Lin, Zheshuai; Huang, Zhipeng; Humphrey, Mark G.; Zhang, Chi

doi:10.1039/d3qi00513e

Cited by 6 publications

(3 citation statements)

References 56 publications

(63 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The vibrational peaks for the SO 4 tetrahedra in the two compounds appeared at about 1200–950 cm –1 and around 610 cm –1 , respectively. These assignments correspond to the reported selenite sulfates. − …”

Section: Resultssupporting

confidence: 84%

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

Zhang,

Wang,

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

The first examples of alkali metal selenite sulfates, namely, Na 8 (SeO 3 )(SO 4 ) 3 (1), Na 2 (H 2 SeO 3 )(SO 4 ) (2), and K 4 (H 2 SeO 3 )-(HSO 4 ) 2 (SO 4 ) (3), were successfully synthesized by hydrothermal reactions. Their structures display three different zero-dimensional configurations composed of isolated sulfate tetrahedra and selenite groups separated by alkali metals. Na 8 (SeO 3 )(SO 4 ) 3 (1) features a noncentrosymmetric structure, while Na 2 (H 2 SeO 3 )(SO 4 ) (2) and K 4 (H 2 SeO 3 )(HSO 4 ) 2 (SO 4 ) (3) are centrosymmetric. Powder secondharmonic-generation measurements revealed that Na 8 (SeO 3 )(SO 4 ) 3 (1) shows a phase-matchable SHG intensity about 1.2 times that of KDP. UV−vis−NIR diffuse reflectance spectroscopic analysis indicated that Na 8 (SeO 3 )(SO 4 ) 3 (1) has a short UV cutoff edge and a large optical band gap, which makes it a possible UV nonlinear optical material. Theoretical calculations revealed that the birefringence of Na 8 (SeO 3 )(SO 4 ) 3 (1) is 0.041 at 532 nm, which is suitable for phasematching condition. This work provides a good experimental foundation for the exploration of new UV nonlinear crystals in an alkali metal selenite sulfate system.

show abstract

Section: Resultssupporting

confidence: 84%

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

Zhang,

Wang,

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…(ii) Through π-conjugated tailoring or the controlled arrangement of anionic groups, for example, K(3-C 5 H 4 NSO 3 )· x H 2 O (0.306@546 nm) and Cs 2 Mg(NH 2 SO 3 ) 4 ·4H 2 O (0.054@546.1 nm) . (iii) Introducing highly polarizable oxyfluoride polyhedral, , such as ZrF 2 (SO 4 ) (0.074@546 nm) and CeF 2 (SO 4 ) (0.36@546 nm) . (iv) Introducing lone-pair electron groups, , for example, CsSb(SO 4 ) 2 (0.174@546 nm) and Nb 2 O 3 (IO 3 ) 2 (SO 4 ) (0.22@1064 nm) .…”

Section: Introductionmentioning

confidence: 99%

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

Li,

Hu,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Sulfate crystals are often criticized for their low birefringence. The small anisotropic SO 4 group is becoming the biggest bottleneck hindering the application of sulfates in optical functional materials. In this study, we report a new method to significantly enhance the birefringence of sulfates. The title compound increases the birefringence recording of sulfates to 0.542@546 nm, which is significantly larger than that of the commercial birefringent crystal of TiO 2 (0.306@546.1 nm). At the infrared wavelength, the birefringence of Hg 4 (Te 2 O 5 )(SO 4 ) can be up to 0.400@1064 nm, which is also much larger than the infrared birefringent crystal of YVO 4 (0.209@1064 nm). In addition, it also has a wide transparency range, high thermal stability, and excellent environmental stability, making it a potential birefringent material. Hg 4 (Te 2 O 5 )(SO 4 ) features a novel two-dimensional layered structure composed of [Hg 4 (Te 2 O 5 )] 2+ layers separated by isolated (SO 4 ) 2− tetrahedra. This compound was designed by introducing a highly selective cation in a tellurite sulfate system. The low valence low coordination cations connect with tellurite groups only, making the sulfate isolated in the structure. The steric repulsive action of the isolated SO 4 tetrahedra may regulate the linear and lone pair groups arranged in a way that favors large birefringence. This method can be proven by theoretical calculations. PAWED studies showed that the large birefringence originated from the synergistic effect of (Hg 2 O 2 ) 2− , (Te 2 O 5 ) 2− , and (SO 4 ) 2− units, with a contribution ratio of 42.17, 37.92, and 19.88%, respectively. Our work breaks the limitation of low birefringence in sulfates and opens up new possibilities for their application as birefringent crystals.

show abstract

“…), − and fluorinated non-π-conjugated units ([BO 4 ], [PO 4 ], [SO 4 ], etc. ), and fluorinated metal-centered polyhedra formed by“fluorination strategy”, − is beneficial for large birefringences, and a series of potential optical materials with enhanced birefringence have been developed accordingly.…”

Section: Introductionmentioning

confidence: 99%

YSO₄F·H₂O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra

Jiao,

Zhang,

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

Birefringent crystals can modulate and detect the polarization of light and are important optical functional materials. The birefringence is positively correlated to the anisotropy of the structure. By partially substituting sulfate anion with large electronegative fluorine in the parent compound Y 2 (SO 4 ) 3 •8H 2 O, a new fluorinated rare-earth sulfate YSO 4 F•H 2 O with enhanced anisotropy was achieved. YSO 4 F•H 2 O features a dense 3D structure constructed by the polarizable [YOF] polyhedra and [SO 4 ]tetrahedra. The diffuse reflectance spectrum reveals that it has a short UV absorption edge of below 200 nm. The substitution of the F − ion enhances the optical anisotropy, making the material exhibit an enhanced birefringence (0.0357 at 546 nm), which is 5.1 times that of the parent compound and is also larger than most deep-UV birefringent sulfates. It is expected that this work may shed useful insights in the exploration of deep-UV birefringent materials with enhanced optical performances..

show abstract

Ce₃F₄(SO₄)₄: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Cited by 6 publications

References 56 publications

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

YSO₄F·H₂O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra

Contact Info

Product

Resources

About

Ce3F4(SO4)4: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Cited by 6 publications

References 56 publications

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

YSO4F·H2O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra

Contact Info

Product

Resources

About

Ce₃F₄(SO₄)₄: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

YSO₄F·H₂O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra