IrF8 Molecular Crystal under High Pressure.

An important goal in chemistry is to prepare F-rich transition metal fluorides due to the high oxidation states and potential applications such as oxidating and fluorinating agents. Thus far, the highest F stoichiometry in the neutral transition metal fluorides is 7. Here, we identify a hitherto unknown IrF8 compound through first-principles swarm-intelligence structure search calculations under high pressure. The three identified IrF8 phases exhibit typical molecular crystal characters, showing +8 oxidation state in Ir. The spatial symmetry of the basic building block in the three IrF8 phases gradually increases with pressure (e.g., dodecahedron [Formula: see text] square antiprism [Formula: see text] quasicube). The pressure-induced faster increase of Ir 5d orbital energy level with respect to F 2p provides a strong charge transfer driving force from Ir 5d to F 2p, facilitating the formation of F-rich compounds. More interestingly, the predicted electron affinities of the three predicted IrF8 phases are comparable/larger than that of PtF6, the strongest oxidation agent in the third row transition metal hexafluorides. The built high-pressure phase diagram of Ir-F binary compounds provides useful information for experimental synthesis.