Bottom-up substitution assembly of AuF<sub>4−</sub><i><sub>n</sub></i><sup>0,−</sup>+<i>n</i>PO<sub>3</sub> (<i>n</i> = 1–4): a theoretical study of novel oxyfluoride hyperhalogen molecules and anions AuF<sub>4−</sub><i><sub>n</sub></i>(PO<sub>3</sub>)<i><sub>n</sub></i><sup>0,−</sup>
Creators: name: Yang, Yi-Fan
name: Cui, Zhong-Hua
name: Ding, Yi-Hong
Publisher: name: Taylor & Francis
Year: 2014
Subjects: subject: Biochemistry
subject: Pharmacology
subject: Evolutionary Biology
subject: FOS: Biological sciences
subject: FOS: Biological sciences
subject: 59999 Environmental Sciences not elsewhere classified
subject: FOS: Earth and related environmental sciences
subject: FOS: Earth and related environmental sciences
subject: 39999 Chemical Sciences not elsewhere classified
subject: FOS: Chemical sciences
subject: FOS: Chemical sciences
subject: Immunology
subject: FOS: Clinical medicine
subject: FOS: Clinical medicine
subject: 69999 Biological Sciences not elsewhere classified
subject: 80699 Information Systems not elsewhere classified
subject: FOS: Computer and information sciences
subject: FOS: Computer and information sciences
subject: Cancer
subject: Hematology

description: Compounds with high electron affinity, i.e. superhalogens, have continued to attract chemists’ attention, due to their potential importance in fundamental chemistry and materials science. It has now proven very effective to build up novel superhalogens with multi-positively charged centres, which are usually called ‘hyperhalogens’. Herein, using AuF<sub>4</sub><sup>−</sup> and PO<sub>3</sub> as the model building blocks, we made the first attempt to design the Au,P-based hyperhalogen anions AuF<sub>4−</sub><i><sub>n</sub></i>(PO<sub>3</sub>)<i><sub>n</sub></i><sup>−</sup> (<i>n</i> = 1–4) at the B3LYP/6-311+G(d)&amp;SDD and CCSD(T)/6-311+G(d)&amp;SDD (single-point) levels (6-311+G(d) for O, F, P and SDD for Au). Notably, for all the considered Au,P systems, the ground state bears a dioxo-bonded structure with <i>n</i> ≤ 3, which is significantly more stable than the usually presumed mono-oxo-bonded one. Moreover, the clustering of the –PO<sub>3</sub> moieties becomes energetically favoured for <i>n</i> ≥ 3. The ground states of AuP<sub>4</sub>O<sub>12</sub><sup>0,−</sup> are the first reported cage-like oxide hyperhalogens. Thus, the −PO<sub>3</sub> moiety cannot be retained during the ‘bottom-up’ assembly. The vertical detachment energy (VDE) value of the most stable AuF<sub>4−</sub><i><sub>n</sub></i>(PO<sub>3</sub>)<i><sub>n</sub></i><sup>−</sup> (<i>n</i> = 1–4) ranges from 7.16 to 8.20 eV, higher than the VDE values of the corresponding building blocks AuF<sub>4</sub><sup>−</sup> (7.08 eV) and PO<sub>3</sub><sup>−</sup> (4.69 eV). The adiabatic detachment energy values of these four hyperhalogens exceed 6.00 eV. Possible generation routes for AuF<sub>4−</sub><i><sub>n</sub></i>(PO<sub>3</sub>)<i><sub>n</sub></i><sup>−</sup> (<i>n</i> = 1–4) were discussed. The presently designed oxyfluorides not only enriches the family of hyperhalogens, but also demonstrates the great importance of considering the structural transformation during the superhalogen → hyperhalogen design such as for the present Au–P based systems.