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Interpreting Effects of Structure Variations Induced by Temperature and Pressure on Luminescence Spectra of Platinum(II) Bis(dithiocarbamate) Compounds
Luminescence spectra of two square-planar dithiocarbamate complexes of platinum(II) with different steric bulk, platinum(II) bis(dimethyldithiocarbamate) (Pt(MeDTC)2) and platinum(II) bis(di(o-pyridyl)dithiocarbamate) (Pt(dopDTC)2), are presented at variable temperature and pressure. The spectra show broad d–d luminescence transitions with maxima at approximately 13500 cm–1 (740 nm). Variations of the solid-state spectra with temperature and pressure reveal intrinsic differences due to subtle variations of molecular and crystal structures, reported at 100 and 296 K for Pt(dopDTC)2. Luminescence maxima of Pt(MeDTC)2 shift to higher energy as temperature increases by +320 cm–1 for an increase by 200 K, mainly caused by a bandwidth increase from 3065 to 4000 cm–1 on the high-energy side of the band over the same temperature range. Luminescence maxima of Pt(dopDTC)2 shift in the opposite direction by −460 cm–1 for a temperature increase by 200 K. The bandwidth of approximately 2900 cm–1 does not vary with temperature. Both ground and emitting-state properties and subtle structural differences between the two compounds lead to this different behavior. Luminescence maxima measured at variable pressure show shifts to higher energy by +47 ± 3 and +11 ± 1 cm–1/kbar, for Pt(MeDTC)2 and Pt(dopDTC)2, respectively, a surprising difference by a factor of 4. The crystal structures indicate that decreasing intermolecular interactions with increasing pressure are likely to contribute to the exceptionally high shift for Pt(MeDTC)2.
Sprache
Englisch
Identifikatoren
ISSN: 0020-1669
eISSN: 1520-510X
DOI: 10.1021/ic5025718
Titel-ID: cdi_proquest_miscellaneous_1674693185
Format
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