Structural Phase Transitions of a Molecular Metal Oxide
Structural Phase Transitions of a Molecular Metal Oxide
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DOI：
10.1002/anie.202010748
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发表时间：
2020-09-30
影响因子：
16.6
通讯作者：
Akutagawa, Tomoyuki
中科院分区：
文献类型：
--
作者：
Fujibayashi, Masaru;Watari, Yu;Akutagawa, Tomoyuki
金属氧化物的结构相随温度和压力而变化。在相变期间，组分离子在多维金属-氧网络中移动。这样的宏观结构事件对颗粒尺寸的变化是鲁棒的，即使在约10 nm的尺度下，并且限制这些转变的尺寸效应在例如铁电体的高密度存储器应用中特别重要。在这项研究中，我们研究了分子金属氧化物[Na@（SO_3）（2）（n-BuPO_3）（4）（Mo_4 Mo_（14）O_（49））-Mo-V-O-VI]（5-）（分子1）在约2nm处的结构转变，通过使用单晶X射线衍射分析。Na（+）包裹在离散的金属氧化物阴离子中，表现出可逆的有序-无序转变，温度引起Mo-O分子骨架的畸变。类似的有序-无序转变也被引发的化学压力所诱导的去除结晶溶剂分子在单晶状态或取代抗衡阳离子，以改变分子包装。
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)(4)(Mo4Mo14O49)-Mo-V-O-VI](5-)(Molecule1) 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.