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The first example of a face-sharing fluoroaluminate anion, Al2F93−, is crystallographically determined in [C18MIm]3[Al2F9](CH2Cl2)1.754 (C18MIm+ = 1-methyl-3-octadecylimidazolium cation), and the geometry and bond properties therein are discussed with the aid of quantum chemical calculations.
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