Phys.org  September 30, 2023
Although Cu2+ is ubiquitous, the relativistic destabilization of the 5d orbitals makes the isoelectronic Au2+ exceedingly rare, typically stabilized only through Au–Au bonding or by using redox non-innocent ligands. An international team of researchers (USA – Stanford University, UC Berkeley, SLAC National Accelerator Laboratory, Lawrence Berkeley National Laboratory, Canada) have developed the perovskite Cs4AuIIAuIII2Cl12, an extended solid with mononuclear Au2+ sites, which is stable to ambient conditions and characterized by single-crystal X-ray diffraction. The 2+ oxidation state of Au was assigned using 197Au Mössbauer spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements, with comparison to paramagnetic and diamagnetic analogues with Cu2+ and Pd2+, respectively, as well as to density functional theory calculations. The gold perovskite offered an opportunity to study the optical and electronic transport of the uncommon Au2+/3+ mixed-valence state and the characteristics of the elusive Au2+ ion coordinated to simple ligands. Compared with the perovskite Cs2AuIAuIIICl6, which has been studied since the 1920s, Cs4AuIIAuIII2Cl12 exhibited a 0.7 eV reduction in optical absorption onset and a 103-fold increase in electronic conductivity… read more. TECHNICAL ARTICLE
Single-crystal XRD structures. Credit: Nature Chemistry (2023)Â