Stabilizing Au2+ in a mixed-valence 3D halide perovskite.

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. Here we report 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. This gold perovskite offers 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 exhibits a 0.7 eV reduction in optical absorption onset and a 103-fold increase in electronic conductivity.

Understanding the Surface Properties of Halide Exchanged Cesium Lead Halide Nanoparticles.

This report describes a characterization study of the surfaces of CsPbBr3 and CsPbBr3- xI x perovskite nanoparticles (NPs) obtained via a simultaneous purification and halide exchange (HE) postsynthetic processing technique. We studied composition-dependent NP-ligand interactions via diffusion ordered NMR (DOSY) and quantified resulting photoluminescence quantum yield (QY) as a function of halide exchange as well as ligand exchange. Importantly, ligand binding strength and QY were found to decrease when successive purification and/or halide/ligand exchange steps were taken without careful concurrent additions of acid and base ligands. This suggests that ligands added during postsynthetic processing steps are localized at the surface of the NP, passivating open surface sites. Further, we show that CsPbBr3- xI x with increasing CsPbI3 character, obtained via the same method, have decreasing ligand density, from 6.4 to 1.4 to 0.2 nm-2, indicating the composition-dependence of surface ligand binding, which also has consequences on the QY of the resulting mixed-halide NPs. These results shed further light on the importance of ion-ligand moiety additions during purification and halide exchange of highly emissive CsPbBr3 NPs to maintain their as-synthesized properties, as well as the intrinsic differences in surfaces binding and photostability between near-unity QY CsPbBr3 and mixed-halide CsPbBr3- xI x NPs.