| Abstract
| - Electronic absorption and 8 T magnetic circular dichroism (MCD) spectra are reported for nitrate salts of Pt(AuPPh3)82+ and Au(AuPPh3)83+ in poly(methyl methacrylate) (PMM) thin films at 295 and 10 K in the vis−UVregion from 1.6 to 3.6 μm-1 (1 μm-1 = 104 cm-1). Enhanced resolution is observed at low temperature, especiallyfor Pt(AuPPh3)82+, which emphasizes the differences in the nature of the low-energy excited configurations andstates between Pt(AuPPh3)82+ and Au(AuPPh3)83+. The absorption and MCD spectra for Pt(AuPPh3)82+ areinterpreted in terms of a combination of excitations from filled Pt 5d orbitals to empty Au framework 6s orbitalsand intraframework Au82+ (IF) transitions, whereas the spectra for Au(AuPPh3)83+ are ascribed entirely to Au IFtransitions.
- Electronic absorption and 8.0 T magnetic circular dichroism (MCD) spectra in the vis−UV region are presented for Pt(AuPPh3)82+ and Au(AuPPh3)83+ in poly(methyl methacrylate) thin films at 295 and 10 K. By means of MO's composed of Au 6s orbitals for the peripheral Au framework atoms and nonbonding 5d orbitals localized on the central Pt atom, the lowest energy bands for Pt(AuPPh3)82+ are attributed to Pt 5d → Au 6s transitions together with intraframework (IF) Au82+ transitions, while those for Au(AuPPh3)83+ are assigned to IF transitions.
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