Evolution of Guanazolium Fluoroaluminates within the Composition-Space Diagram and with the Temperature
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- 作者：Amandine Cadiau ; Armel Le Bail ; Annie Hmon-Ribaud ; Marc Leblanc ; Monique Body ; Franck Fayon ; Etienne Durand ; Jean-Claude Boulou ; Vincent Maisonneuve
- 刊名：Crystal Growth & Design
- 出版年：2010
- 出版时间：December 1, 2010
- 年：2010
- 卷：10
- 期：12
- 页码：5159-5168
- 全文大小：1242K
- 年卷期：v.10,no.12(December 1, 2010)
- ISSN：1528-7505
文摘
The 2D composition-space diagram of the Al(OH)3−Am2TAZ−HFaq−ethanol system is established under microwave heating at 190 °C for [Al3+] = 1 mol·L−1. Four new fluoroaluminates are evidenced when the [HF]/[Am2TAZ] ratio is increased in the starting solution, and the dimensionality of the inorganic frameworks is increased from 0D in [HAm2TAZ]2·(AlF5(H2O))·2H2O (Pc, Z = 2), to 1D in [HAm2TAZ]2·(AlF5) and [HAm2TAZ]2·(Al2F8) (Fdd2, Z = 8), and to 2D in [HAm2TAZ]2·(Al5F17) (Imm2, Z = 2). This evolution is partially paralleled by the thermal decomposition of [HAm2TAZ]2·(AlF5(H2O))·2H2O; on heating, this hydrate gives [HAm2TAZ]2·(AlF5) at 100−150 °C and [HAm2TAZ]2·(Al2F8) at 180 °C; the loss and simultaneous decomposition of [HAm2TAZ]F leave a solid residue of polymeric paracyanogen (CN)2n that is further decomposed and hydrolyzed into HCN and HNCO by atmospheric water traces. NMR 19F spectroscopy of [HAm2TAZ]2·(AlF5) is in agreement with the crystallographic determination, and the 27Al spectrum demonstrates that a significant F−/OH− substitution is excluded.