Evidence of New Fluorinated Coordination Compounds in the Composition Space Diagram of FeF3/ZnF2鈥揌amtetraz-HFaq System

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• 作者：Vanessa Pimenta ; J茅r么me Lhoste ; Annie H茅mon-Ribaud ; Marc Leblanc ; Jean-Marc Gren猫che ; Laurent Jouffret ; Arnaud Martel ; Gilles Dujardin ; Vincent Maisonneuve
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：September 2, 2015
• 年：2015
• 卷：15
• 期：9
• 页码：4248-4255
• 全文大小：659K
• ISSN：1528-7505

文摘

The exploration of the composition space diagram of the FeF₃/ZnF₂鈥揌amtetraz-HF_aq system (Hamtetraz = 5-aminotetrazole) by solvothermal synthesis at 160 掳C for 72 h in dimethylformamide (DMF) has evidenced five new hybrid fluorides (1鈥?b>5); the structures are characterized from single crystal X-ray diffraction data. [Hdma]路(ZnFe^III(H₂O)₄F₆) (1) and [Hdma]路[Hgua]₂路(Fe^IIIF₆) (2) contain anionic inorganic chains (1) or isolated octahedra (2) weakly hydrogen bonded (Class I hybrids) to dimethylammonium (Hdma) and/or guanidinium (Hgua) cations which are produced from the tetrazole ligand and solvent decomposition. [Hdma]₂路[Hgua]路[NH₄]路[ZnFe^IIIF₅(amtetraz)₂]₂ (3), [Hdma]₂路[Zn_1.6Fe^II_0.4Fe^IIIF₆(amtetraz)₃] (4), and [Hdma]路[Zn₄F₅(amtetraz)₄] (5) are considered as Class II hybrids in which the (amtetraz)^{鈭?/sup> anions are strongly linked to divalent metal cations via N鈥揗 bonds. In 3, _{鈭?/sub>{[NH4]路[ZnFeIIIF5(amtetraz)2]2} layers are separated by [Hdma]+ and [Hgua]+ cations. 4 and 5 exhibit three-dimensional (3D) hybrid networks that contain small cavities where [Hdma]+ cations are inserted. A porous 3D metal鈥搊rganic framework intermediate is evidenced from the thermogravimetric analysis and X-ray thermodiffraction of 5.}}