Unprecedented v-shaped [SeO2E] units stabilized in KM[Se2O5]2[SeO2] (M= Al and Ga) constructed by nanoconfinement strategy
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PUBLIC SUMMARY
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The first [SeO2]-type selenite, KM[Se2O5]2[SeO2] (M= Al, Ga) were synthesized.
The strong polarization of [SeO2] largely improves second harmonic generation and birefringence of selenite.
KM[Se2O5]2[SeO2] exhibit excellent properties and are promising NLO crystals.
Unprecedented [SeO2] units bring selenites structural chemistry into a new era.
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ABSTRACT
Pyramidal [SeO3E]2- (E being a lone pair) selenite units with stereochemically active lone pairs (SCALP) have been widely used for the design of nonlinear optical (NLO) materials with large second harmonic generation (SHG) response. However, compared with the sp3 hybridization pyramidal [SeO3E]2- units, primitive V-shaped sp2 hybridization [SeO2E] units containing not only SCALP but also the delocalized π-electrons are more conducive to excellent NLO performances. But up to now, no crystalline selenites containing V-shaped [SeO2E] groups have been reported because of the fact when the acid SeO2 gaseous molecule reacts with a basic oxide molecule, the V-shaped [SeO2E] unit typically transforms into the pyramidal [SeO3E]2- units. Herein, through constructing three-dimension (3D) ordered electrically-neutral nanopores in K-Al/Ga-Se-O framework to ‘adsorb’ SeO2 gaseous molecule, the first selenites containing the [SeO2E] units, KGa[Se2O5]2[SeO2] (I) and KAl[Se2O5]2[SeO2] (II) were designed and synthesized successfully. Theoretical calculations and experimental results indicate that they both exhibit excellent NLO properties, including the largest SHG response ((I)~10.2×KDP, (II)~11.5×KDP) and birefringence (Δn(I)=0.196@546 nm; Δn(II)=0.208@546 nm) in selenites that have no d0 transition metal (TM) and other stereochemically active lone pair cations, suggesting their immense potential as NLO crystals. -
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REFERENCES
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Zheng Y., Li Q., Wu H., et al. (2025). Unprecedented v-shaped [SeO2E] units stabilized in KM[Se2O5]2[SeO2] (M= Al and Ga) constructed by nanoconfinement strategy. The Innovation Materials 3:100160. https://doi.org/10.59717/j.xinn-mater.2025.100160
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Zheng Y., Li Q., Wu H., et al. (2025). Unprecedented v-shaped [SeO2E] units stabilized in KM[Se2O5]2[SeO2] (M= Al and Ga) constructed by nanoconfinement strategy. The Innovation Materials 3:100160. https://doi.org/10.59717/j.xinn-mater.2025.100160
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Figure 1.
Electron density difference (EDD) analysis of Se(5) and O(9), with blue indicating a decrease in electron density and yellow indicating an increase.
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Figure 2.
The Crystal structure of (I)
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Figure 3.
The chiral structural features of the compound (I)
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Figure 4.
Spectroscopic and optical properties
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Figure 5.
Birefringence, SHG and bandgap of the reported NCS selenites without d0 TM and other stereochemically active lone pair cations.
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Figure 6.
Theoretical calculations
