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23 in ref 1.
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79960888738
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The IUPAC numbering scheme for pyrene differs from that used in ref 1 such that the compound listed there as 3-pyrenecarboxylic acid is now named 1-pyrenecarboxylic acid.
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The IUPAC numbering scheme for pyrene differs from that used in ref 1 such that the compound listed there as 3-pyrenecarboxylic acid is now named 1-pyrenecarboxylic acid.
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26
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79960865493
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RW also reported data with 2-pyrenecarboxylic acid (referred to as the 4-isomer in ref 1) as an excited-state electron acceptor. This compound was not reinvestigated here because of its structural similarity to 1-pyrenecarboxylic acid and because the driving force range of its quenching experiments overlaps that of the other acceptors and is, therefore, not distinctive.
-
RW also reported data with 2-pyrenecarboxylic acid (referred to as the 4-isomer in ref 1) as an excited-state electron acceptor. This compound was not reinvestigated here because of its structural similarity to 1-pyrenecarboxylic acid and because the driving force range of its quenching experiments overlaps that of the other acceptors and is, therefore, not distinctive.
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In some cases, interception of an exciplex by a second donor molecule may lead to emission from the 2:1 exciplex and, in others, to exciplex quenching via faster return electron transfer. For an example of the latter, see ref 13b and references therein.
-
In some cases, interception of an exciplex by a second donor molecule may lead to emission from the 2:1 exciplex and, in others, to exciplex quenching via faster return electron transfer. For an example of the latter, see ref 13b and references therein.
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excit) for electron transfer quenching of excited DMA with BN of +0.34 eV.
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excit) for electron transfer quenching of excited DMA with BN of +0.34 eV.
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79960871584
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A number of experiments in both the solid state and solution demonstrate that at least one of the methoxy groups in neutral 1,2,3-trimethoxybenzene is twisted out of conjugation with the aromatic ring. (17) In contrast, MO calculations (B3LYP/6-311+G) show that all three methoxy groups in the radical cation are aligned for conjugation (see the Supporting Information).
-
A number of experiments in both the solid state and solution demonstrate that at least one of the methoxy groups in neutral 1,2,3-trimethoxybenzene is twisted out of conjugation with the aromatic ring. (17) In contrast, MO calculations (B3LYP/6-311+G) show that all three methoxy groups in the radical cation are aligned for conjugation (see the Supporting Information).
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79960874926
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s associated with the SSRIP is ∼1 eV larger than for an ion pair at contact. (5a) In contrast, for Δ G values less negative than -0.4 eV, numerous analyses (6d, 6h, 6j, 6k, 6m, 6o) in polar solvents of low viscosity support the adequacy of a simple encounter complex or contact electron transfer model.
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s associated with the SSRIP is ∼1 eV larger than for an ion pair at contact. (5a) In contrast, for Δ G values less negative than -0.4 eV, numerous analyses (6d, 6h, 6j, 6k, 6m, 6o) in polar solvents of low viscosity support the adequacy of a simple encounter complex or contact electron transfer model.
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47
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79960864110
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Detecting weak exciplex emissions at the time of the original RW work would not have been easy, if at all possible. Digital recording of fluorometry data was not available 40 years ago, and instruments were far less sensitive. Since then, the much lower dark count of photomultiplier tubes and the ease of manipulating the data digitally, e.g., by curve subtraction and logarithmic plots, have made it practical to detect such weak exciplex emissions at the tail of the much stronger residual monomer fluorescence (see Figure 4 and the Supporting Information).
-
Detecting weak exciplex emissions at the time of the original RW work would not have been easy, if at all possible. Digital recording of fluorometry data was not available 40 years ago, and instruments were far less sensitive. Since then, the much lower dark count of photomultiplier tubes and the ease of manipulating the data digitally, e.g., by curve subtraction and logarithmic plots, have made it practical to detect such weak exciplex emissions at the tail of the much stronger residual monomer fluorescence (see Figure 4 and the Supporting Information).
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