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. 2022 Oct 27;13(42):9883-9888.
doi: 10.1021/acs.jpclett.2c02582. Epub 2022 Oct 17.

A Chemical-Pressure-Induced Phase Transition Controlled by Lone Electron Pair Activity

Eduardo O Gomes  1 , Amanda F Gouveia  1 , Lourdes Gracia  1   2 , Álvaro Lobato  3 , J Manuel Recio  4 , Juan Andrés  5
Affiliations

A Chemical-Pressure-Induced Phase Transition Controlled by Lone Electron Pair Activity

Eduardo O Gomes et al. J Phys Chem Lett. .

Abstract

The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the β → α pressure-induced phase transition in SnMoO4 and the substitution process of Mo6+ by W6+ in SnMo1-xWxO4 solid solutions (x = 0-1). Special attention is paid to discriminating the role of the lone pair Sn2+ cation from the structural distortive effect along the Mo/W substitution process, which is crucial to disentangle the driven force of the transition phase. Furthermore, the reverse α → β transition observed at high temperature in SnWO4 is rationalized on the same basis as a negative pressure effect associated with a decreasing of W6+ percentage in the solid solution. This work opens a versatile chemical approach in which the types of interactions along the formation of solid solutions are clearly differentiated and can also be used to tune their properties, providing opportunities for the development of new materials.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Expected energy-volume scenario highlighting potential pressure-, composition-, and temperature-induced transitions in the SnMo1–xWxO4 solid solution. Arrows from top to bottom indicate phases connected across these transitions.
Figure 2
Figure 2
Polyhedral view of the β (left) and α (right) unit cells. SnO6 (β) and SnO8 (α) polyhedra are shown in green, whereas [TO4] tetrahedra are depicted in blue.
Figure 3
Figure 3
Pressure and temperature regions of α and β stability for both SnMoO4 and SnWO4 compounds.
Figure 4
Figure 4
Chemical pressure-physical pressure correspondence for the SnWO4 (purple) and SnMoO4 (green) pure compounds.
Figure 5
Figure 5
Extended MO energy diagram for the Sn-Ob-T interaction.
See this image and copyright information in PMC

References

    1. Badding J. V. High-pressure Synthesis, Characterization and Tuning of Solid State Materials. Annu. Rev. Mater. Sci. 1998, 28, 631–658. 10.1146/annurev.matsci.28.1.631. - DOI
    1. Brazhkin V. V. High-pressure Synthesized Materials: Treasures and Hints. High Press. Res. 2007, 27, 333–351. 10.1080/08957950701546956. - DOI
    1. Li X.; Fu Y.; Pedesseau L.; Guo P.; Cuthriell S.; Hadar I.; Even J.; Katan C.; Stoumpos C. C.; Schaller R. D.; et al. Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening. J. Am. Chem. Soc. 2020, 142, 11486–11496. 10.1021/jacs.0c03860. - DOI - PubMed
    1. Wang Y.; Zhang L.; Wang J.; Li Q.; Wang H.; Gu L.; Chen J.; Deng J.; Lin K.; Huang L.; et al. Chemical-Pressure-Modulated BaTiO3 Thin Films with Large Spontaneous Polarization and High Curie Temperature. J. Am. Chem. Soc. 2021, 143, 6491–6497. 10.1021/jacs.1c00605. - DOI - PubMed
    1. Lin K.; Li Q.; Yu R.; Chen J.; Attfield J. P.; Xing X. Chemical Pressure in Functional Materials. Chem. Soc. Rev. 2022, 51, 5351–5364. 10.1039/D1CS00563D. - DOI - PubMed