Structural Phase Transitions of a Molecular Metal Oxide

Masaru Fujibayashi, Yu Watari, Ryo Tsunashima, Sadafumi Nishihara, Shin ichiro Noro, Chang Gen Lin, Yu Fei Song, Kiyonori Takahashi, Takayoshi Nakamura, Tomoyuki Akutagawa

Research output: Contribution to journalArticlepeer-review

Abstract

The structural phase of a metal oxide changes with temperature and pressure. During phase transitions, component ions move in multidimensional metal–oxygen networks. Such macroscopic structural events are robust to changes in particle size, even at scales of around 10 nm, and size effects limiting these transitions are particularly important in, for example, high-density memory applications of ferroelectrics. In this study, we examined structural transitions of the molecular metal oxide [Na@(SO3)2(n-BuPO3)4MoV4MoVI14O49]5− (Molecule 1) at approximately 2 nm by using single-crystal X-ray diffraction analysis. The Na+ encapsulated in the discrete metal-oxide anion exhibited a reversible order–disorder transition with distortion of the Mo–O molecular framework induced by temperature. Similar order–disorder transitions were also triggered by chemical pressure induced by removing crystalline solvent molecules in the single-crystal state or by substituting the countercation to change the molecular packing.

Original languageEnglish
Pages (from-to)22446-22450
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number50
DOIs
Publication statusPublished - 2020 Dec 7

Keywords

  • cage compounds
  • crystal engineering
  • molybdenum
  • phase transitions
  • polyoxometalates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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