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4 was chosen as a solvent because precipitation of compounds o2c and g2c is observed after approximately 30 min for the solution of both o2c and g2c in MCH, respectively.
-
4 was chosen as a solvent because precipitation of compounds o2c and g2c is observed after approximately 30 min for the solution of both o2c and g2c in MCH, respectively.
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92
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Notably, all UV/vis absorption spectra show a small blue shift with increasing temperature, and a slightly reduced peak intensity for the absorption maximum. These spectral changes are observed for both the monomelic and dimeric series as well as for the respective reference compounds without calix[4]arene substitution see Figures S12 and S13 in the Supporting Information, Hence, the observed effects appear to be independent of the respective PBI unit as well as the calix[4]arene substitution on the chromophore. We attribute the hypsochromic shift to a decrease of the dielectric constant of CCl4 with increasing temperature,35 and the reduced absorption coefficient is attributed to the broadening of the absorption band due to the population of more conformations at higher temperature
-
35 and the reduced absorption coefficient is attributed to the broadening of the absorption band due to the population of more conformations at higher temperature.
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93
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This is supported by the fact that, for compound oref, a hypsochromic shift of the band maximum from 523 nm in CCl4 (with a relative permittivity of ε@293 K, 2.24) to 517 nm (ε@293 K, 2.02) in MCH is observed. Hence, lowering the solvent polarity of Δε ≈ 0.2 leads to a spectral shift of about 6 nm. For the permittivity of CCl 4 at 343 K, a value of ε, 2.14 is given, and, accordingly, an increase of temperature between 293 and 343 K leads to a reduced permittivity of Δε ≈ 0.1, resulting in a hypsochromic shift of the band maximum of 3 nm from 523 nm (T, 293 K) to 520 nm (T, 343 K, Similar behavior is also found for compound gref (with 17 nm shift upon solvent change with Δε RS 0.2, and with 8 nm shift upon temperature change with Δε ≈ 0.1) and compound rref with 11 nm shift upon solvent change with Δε ≈ 0.2, and with 5 nm shift upon temperatur
-
4 at 343 K, a value of ε = 2.14 is given, and, accordingly, an increase of temperature between 293 and 343 K leads to a reduced permittivity of Δε ≈ 0.1, resulting in a hypsochromic shift of the band maximum of 3 nm from 523 nm (T = 293 K) to 520 nm (T = 343 K). Similar behavior is also found for compound gref (with 17 nm shift upon solvent change with Δε RS 0.2, and with 8 nm shift upon temperature change with Δε ≈ 0.1) and compound rref (with 11 nm shift upon solvent change with Δε ≈ 0.2, and with 5 nm shift upon temperature change with Δε ≈ 0.1). For temperature-dependent permittivity values, see CRC Handbook of Chemistry and Physics, 76th ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, FL, 1995.
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24c In contrast, the orange reference compound oref reveals quantum yields of almost unity in all five solvents (see Table 1).
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24c In contrast, the orange reference compound oref reveals quantum yields of almost unity in all five solvents (see Table 1).
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Longer-lived excited states due to PBI-excimer formation have been reported in the literature; see (a) Katoh, R.; Sinha, S.; Murata, S.; Tachiya, M. J. Photochem. Photobiol., A 2001, 145, 23-34.
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For all lifetimes determined for compounds g2c, gc, and gref, biexponential decays are observed. Accordingly, additional small components of ca. 0.5 ns are found for each compound independent of the solvent polarity and of the calix[4]arene substitution of the chromophore. The latter components are thus considered to be independent of the calix[4]arene substitution of the dye unit and are inherent to the green PBI chromophore itself (for details refer to Table 3).
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Solutions of o2c and oc in the lowest polarity solvent MCH could not be measured due to precipitation of the compounds.
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Solutions of o2c and oc in the lowest polarity solvent MCH could not be measured due to precipitation of the compounds.
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Global and target analysis can be performed with, e.g, the R package TIMP; see
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(d) Global and target analysis can be performed with, e.g., the R package TIMP; see http://cran.r-project.org/doc/packages/TIMP.pdf.
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An excited-state charge transfer process resulting in a charge transfer state of the jr-stacked form could not be unambiguously confirmed by global and target analysis
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An excited-state charge transfer process resulting in a charge transfer state of the jr-stacked form could not be unambiguously confirmed by global and target analysis.
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