4.8 Article

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

Journal

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 13, Issue 42, Pages 9883-9888

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c02582

Keywords

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Funding

  1. Spanish MCIU [PGC2018-094417-B-I00, PGC2018-094814 -B-C1, PGC2018-094814 -B-C2, RED2018-102612-T]
  2. Spanish MINECO [PGC2018-094417-B-I00, PGC2018-094814 -B-C1, PGC2018-094814 -B-C2, RED2018-102612-T]
  3. Universitat Jaume I [POSDOC/2019/30, UJI-B2019-30]
  4. Principado de Asturias (FICYT) [AYUD/2021/51036]
  5. FEDER [AYUD/2021/51036]
  6. Generalitat Valenciana [2018/064]

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This study explores the correlation between phase transitions in SnMoO4 and SnMo1-xWxO4 solid solutions, demonstrating the importance of the chemical pressure approach for property control in functional materials. The research reveals the potential of tuning material properties through the Mo/W substitution process.
The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the beta -> alpha 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 alpha -> beta 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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