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Fig. 9.9 Pt 4f
7/2
and 4f
5/2
core level spectra for (a) [Pt
2
(EtCS
2
)
4
I]
1
(2), (b) [Pt
2
(EtCS
2
)
4
], and
(c) [Pt
2
(EtCS
2
)
4
I
2
][
32
]
Binding energies of the Pt 4f
7/2
and 4f
5/2
core levels are summarized in Table
9.2
.
The Pt 4f
7/2
and 4f
5/2
peaks of 2 are broad compared to those of [Pt
2
(EtCS
2
)
4
] and
[Pt
2
(EtCS
2
)
4
I
2
] and can be resolved into Pt
2+
4f
7/2,5/2
and Pt
3+
4f
7/2,5/2
doublets using
a curve deconvolution employing a Gaussian-Lorenztian line shape fit. The energies
of each resolved doublet agree well with those observed for [Pt
2
(EtCS
2
)
4
] and
[Pt
2
(EtCS
2
)
4
I
2
]. It is apparent that the compounds 1 and 2 in the metallic state
exist not in the averaged-valence state of Pt
2.5+
but in the mixed-valence state
composed of Pt
2+
and Pt
3+
on the timescale of XPS spectroscopy (ca. 10
17
s).
The intensity of the Pt
3+
4f
7/2,5/2
doublet is weak relative to that of Pt
2+
. This may be
due to the reduction of Pt
3+
to Pt
2+
by X-ray irradiation.
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