Synthesis and solid-state structural characterization of a series of aqueous heterometallic tridecameric group 13 clusters.
Synthesis and solid-state structural characterization of a series of aqueous heterometallic tridecameric group 13 clusters.
复制标题
一系列水性异金属十三聚族簇的合成和固态结构表征。
DOI：
10.1021/acs.inorgchem.5b00097
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发表时间：
2015
影响因子：
4.6
通讯作者：
Darren W. Johnson
中科院分区：
文献类型：
--
作者：
Maisha K. Kamunde;Dylan B. Fast;Zachary L. Mensinger;Jason T. Gatlin;L. Zakharov;M. Dolgos;Darren W. Johnson
介绍了一系列新型异金属水相纳米级镓/铟三聚体簇的合成和固态表征。这些羟基水基极大地扩展了离散的13水基簇库。本报告详细介绍了这些化合物的合成和结构特征，它们是薄膜氧化物材料应用的前驱体（油墨）。单晶x射线衍射（XRD）数据表明，这些簇的六方晶胞长度在a， b = 20.134-20.694 Å和c = 18.266-18.490 Å范围内。随着铟占用量的增加，单体电池体积增大（V = 6494-6774 A(3)）。通过电子探针微量分析和元素分析确定了几种Ga/In簇的组成与单晶XRD结果一致。采用变温粉末XRD研究了Ga/In簇在高温下向金属氧化物的转变。随着加热，铟占比较低的Ga/In簇转变为β-Ga2O3结构。对于铟占比较高的团簇，会发生相分离，形成In2O3 bixbyite型结构。由于这些异金属溶液前体的可调性，本文所展示的分子水平上的化学计量学控制对于设计金属氧化物的功能薄膜是重要的。此外，关于这些化合物的固态结构的信息导致对这些簇的材料特性的基本理解，为未来的薄膜和前驱体的发展提供了基础。
The synthesis and solid-state characterization of a complete series of new heterometallic aqueous nanoscale Ga/In tridecameric clusters is presented. These hydroxo-aquo species significantly expand the library of discrete, aqueous group 13 clusters. This report details the synthetic and structural characterization of these compounds, which are of interest as precursors (inks) for thin-film oxides with materials applications. Single-crystal X-ray diffraction (XRD) data show that the hexagonal unit cell lengths of these clusters fall within the range a, b = 20.134-20.694 Å and c = 18.266-18.490 Å. The unit cell volumes become larger (V = 6494-6774 A(3)) with increasing indium occupancy. The compositions of several Ga/In clusters determined by electron probe microanalysis and elemental analysis are in agreement with single-crystal XRD results. The transformation of the Ga/In clusters to metal oxides at high temperature was studied using variable-temperature powder XRD. With heating, the Ga/In clusters with lower indium occupancies convert to the β-Ga2O3 structure. For clusters with higher indium occupancies, phase separation occurs, and an In2O3 bixbyite-type structure forms. The stoichiometric control at the molecular level demonstrated herein is important in designing functional thin films of metal oxides due to the tunable nature of these heterometallic solution precursors. In addition, information about the solid-state structure of these compounds leads to a fundamental understanding of the materials properties of these clusters for future thin-film and precursor development.