Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization

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

doi:10.1002/advs.202306670

Cited by 7 publications

(2 citation statements)

References 93 publications

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“…Through structural analysis, we can find that the SO 4 tetrahedron is a high valence, low coordination group. Compared with the sulfate group, tellurite groups belong to low valence low coordination group. , According to Pauling’s fourth rule, the balance cations tend to connect with tellurite groups rather than the SO 4 tetrahedra. The reported metal tellurite sulfate compounds also confirmed the selectivity of the balance cations.…”

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.

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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.

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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.

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“…Birefringent crystals are key materials used in the production of optical devices, including polarizers, optical isolators, circulators, and phase retarders. 1–7 Inorganic phosphate crystals, known for their short ultraviolet cutoff edges and good crystal growth habits, represent a classic optoelectronic material. 8–13 KDP (KH 2 PO 4 ) and KTP (KTiPO 4 ) are quintessential examples of phosphates, boasting significant application as nonlinear optical (NLO) materials.…”

Section: Introductionmentioning

confidence: 99%

Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks

Xu,

Chen,

et al. 2024

Inorg. Chem. Front.

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Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering

Zhou,

Cheng,

Chu

et al. 2024

Angewandte Chemie

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Deep‐ultraviolet (UV) birefringent materials are urgently needed to facilitate light polarization in deep‐UV lithography. Maximizing anisotropy by regulating the alignment of functional modules is essential for improving the linear optical performance of birefringent materials. In this work, we proposed a strategy to design deep‐UV birefringent materials that achieve functional module ordering via weak interactions. Following this strategy, four compounds CN4H7SO3CF3, CN4H7SO3CH3, C(NH2)3SO3CH3, and C(NH2)3SO3CF3 were identified as high‐performance candidates for deep‐UV birefringent materials. The millimeter‐sized crystals of CN4H7SO3CF3, CN4H7SO3CH3, and C(NH2)3SO3CH3 were grown, and the transmittance spectra show that their cutoff edges are below 200 nm. CN4H7SO3CF3 exhibits the largest birefringence (0.149 @ 546 nm, 0.395 @ 200 nm) in the deep‐UV region among reported sulfates and sulfate derivatives. It reveals that the hydrogen bond can modulate the module ordering of the heteroleptic tetrahedra and planar π‐conjugated cations, thus greatly enhancing the birefringence. Our study not only discovers new deep‐UV birefringent materials but also provides an upgraded strategy for optimizing optical anisotropy to achieve efficient birefringence.

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Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization

Cited by 7 publications

References 93 publications

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

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

Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks

Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering

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Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization

Cited by 7 publications

References 93 publications

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

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

Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks

Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering

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Product

Resources

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

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