Spectroscopic characterization of a series of platinum acetylide complexes having a localized triplet exciton |
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Authors: | Cooper Thomas M Krein Douglas M Burke Aaron R McLean Daniel G Rogers Joy E Slagle Jonathan E Fleitz Paul A |
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Institution: | Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433, USA. Thomas.Cooper@wpafb.af.mil |
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Abstract: | In this work, we describe the spectroscopic properties of a series of platinum complexes containing one acetylide ligand per platinum, having the chemical formula trans-Pt(PBu(3))(2)((Ctriple bond]CC(6)H(4))(n)()-H)Cl, n = 1-3 (designated as half-PEn-Pt) and compare their spectroscopic behavior with the well-characterized series trans-Pt(PBu(3))(2)((Ctriple bond]CC(6)H(4))(n)-H)(2), n = 1-3 (designated as PEn-Pt). This comparison aims to determine if the triplet state of PEn-Pt is confined to one ligand or delocalized across the central platinum atom. We measured ground-state absorption spectra, fluorescence spectra, phosphorescence spectra, and triplet-state absorption spectra. The ground-state absorption spectra and fluorescence spectra both showed a blue shift when comparing half-PEn-Pt with PEn-Pt, showing the S(1) state is delocalized across the platinum. In contrast, the phosphorescence spectra of the two types of compounds had the same 0-0 band energy, showing the T(1) state was confined to one ligand in PEn-Pt. The triplet state absorption spectra blue shifted when comparing half-PEn-Pt with PEn-Pt, showing the T(n) state was delocalized across the central platinum. This comparison supports recently published work that suggested this confinement effect (Rogers, J. E et al. J. Chem. Phys. 2005, 122, 214701). |
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