학술논문
Stabilizing Au 2+ in a mixed-valence 3D halide perovskite.
Document Type
Academic Journal
Author
Lindquist KP; Department of Chemistry, Stanford University, Stanford, CA, USA.; Eghdami A; Department of Physics, University of California Berkeley, Berkeley, CA, USA.; Deschene CR; Department of Chemistry, Stanford University, Stanford, CA, USA.; Heyer AJ; Department of Chemistry, Stanford University, Stanford, CA, USA.; Wen J; Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.; Smith AG; Department of Physics, University of California Berkeley, Berkeley, CA, USA.; Solomon EI; Department of Chemistry, Stanford University, Stanford, CA, USA.; Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, CA, USA.; Lee YS; Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.; Department of Applied Physics, Stanford University, Stanford, CA, USA.; Neaton JB; Department of Physics, University of California Berkeley, Berkeley, CA, USA.; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.; Kavli Energy NanoSciences Institute at Berkeley, Berkeley, CA, USA.; Ryan DH; Physics Department and Centre for the Physics of Materials, McGill University, Montreal, Quebec, Canada.; Karunadasa HI; Department of Chemistry, Stanford University, Stanford, CA, USA. hemamala@stanford.edu.; Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. hemamala@stanford.edu.
Source
Publisher: Nature Pub. Group Country of Publication: England NLM ID: 101499734 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1755-4349 (Electronic) Linking ISSN: 17554330 NLM ISO Abbreviation: Nat Chem Subsets: PubMed not MEDLINE; MEDLINE
Subject
Language
English
Abstract
Although Cu 2+ is ubiquitous, the relativistic destabilization of the 5d orbitals makes the isoelectronic Au 2+ exceedingly rare, typically stabilized only through Au-Au bonding or by using redox non-innocent ligands. Here we report the perovskite Cs 4 Au II Au III 2 Cl 12 , an extended solid with mononuclear Au 2+ sites, which is stable to ambient conditions and characterized by single-crystal X-ray diffraction. The 2+ oxidation state of Au was assigned using 197 Au Mössbauer spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements, with comparison to paramagnetic and diamagnetic analogues with Cu 2+ and Pd 2+ , 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 Au 2+/3+ mixed-valence state and the characteristics of the elusive Au 2+ ion coordinated to simple ligands. Compared with the perovskite Cs 2 Au I Au III Cl 6 , which has been studied since the 1920s, Cs 4 Au II Au III 2 Cl 12 exhibits a 0.7 eV reduction in optical absorption onset and a 10 3 -fold increase in electronic conductivity.
(© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)
(© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)