On the halide aggregation into the [Au 4 (PPh 3 ) 4 ] 4+ cluster core. Insights from structural, optical and interaction energy analysis in [(Ph 3 PAu) 4 X 2 ] 2+ and [(Ph 3 PAu) 4 X] 3+ species (X = Cl - , Br - , I - )

The aggregation of halide atoms into gold clusters offers an interesting scenario for the development of novel metal-based cavities for anion recognition and sensing applications. Thus, further understanding of the different contributing terms leading to efficient cluster-halide aggregation is relevant to guide their synthetic design. In this report, we evaluate the formation of [(Ph PAu) X ] and [(Ph PAu) X] species (X = Cl , Br , I ) in terms of different energy contributions underlying the stabilization of the cluster-halide interaction, and the expected UV-vis absorption profiles as a result of the variation in frontier orbital arrangements. Our results denote that a non-planar Au core shape enables enhanced halide aggregation, which is similar for Cl , Br , and I , in comparison to the hypothetical planar Au counterparts. The electrostatic nature of the interaction involves a decreasing ion-dipole term along with the series, and for iodine species, higher-order electrostatic contributions become more relevant. Hence, the obtained results help in gaining further understanding of the different stabilizing and destabilizing contributions to suitable cluster-based cavities for the incorporation of different monoatomic anions.