2408
T. Kindahl et al. / Tetrahedron Letters 54 (2013) 2403–2408
geometry, and as the force cut-off values were in fact met, this can-
not be said for certain.
References and notes
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Time-dependent DFT (TD-DFT) calculations using unrestricted
B3LYP and CAM-B3LYP47 methods were performed to obtain
triplet–triplet excitation energies and oscillator strengths (f).
The results are summarized in Table 1, where the wavelengths
are given for all excitations at a longer wavelength than 400 nm
and f >0.4. Except for the B3LYP result for 1, which shows two
rather strong excitations (f = 1.79 and 1.30, at 643 and 695 nm),
the two methods yield only one dominant triplet excitation for
each structure, with oscillator strength in the range of 1.4–3.1.
The B3LYP result for 2 shows its most intense excitation at
657 nm, with two weaker excitations close to that value. If the
triplet absorption is indeed a very important parameter for effi-
cient OPL in these compounds, the B3LYP calculated wavelengths
are somewhat too long to reflect the OPL results. For instance, the
best OPL effect at 532 and 600 nm would be expected for 3 and 4,
respectively. This is not in accord with the OPL results, although
the oscillator strengths follow better OPL transmission levels if
summed over the excitations in Table 1 (two excitations for 1
and three for 2). The order of increasing wavelength for the struc-
tures from the B3LYP calculations is 3 < 4 < 1 ꢀ 2. The same order
is obtained from the CAM-B3LYP method, although the dominant
excitations are shifted toward shorter wavelengths and span from
471 nm for 3 to 580 nm for 2. The CAM-B3LYP results correspond
better with the OPL data at 532 and 600 nm for both wavelengths
and oscillator strengths. However, experimental kmax TT values
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CAM-B3LYP value of 497 nm, which suggests that interpretations
must be performed with caution since many factors such as sol-
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This Letter, along with others, suggests that the OPL effect can
be enhanced by incorporation of
p-electron donor groups into a
Pt(II)-alkyne structure,11,15,49 and that the stronger reverse satura-
ble absorption (at a specific wavelength) that results from the
incorporation, likely depends more on a high triplet excited-state
absorption cross section rather than on other factors such as a long
triplet state lifetime.
In summary, OPL data of Pt(II) compounds 1–3 indicate that
particularly 2, but also 1, or compounds with similar structural fea-
tures, should be considered for further processing toward optical
limiting filters. The Pt(II) compounds can be obtained in high yields
via existing synthesis methods. Since reverse saturable absorption
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Acknowledgments
Financial support to B.E. by the Swedish Defence Research
Agency (FOI), and to T.K. from the Kempe Foundations is gratefully
acknowledged. We thank the High Performance Computing Center
North (HPC2N) for computational resources.
Supplementary data
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Supplementary data (synthesis and chemical characterization
of compounds) associated with this article can be found, in the on-