Comparative analysis of the energy levels of planar and core-twisted perylene bisimides in solution and solid state by UV/VIS, CV, and UPS/IPES |
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Authors: | C Arantes M Scholz R Schmidt V Dehm M L M Rocco A Schöll F Reinert F Würthner |
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Institution: | 1. Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909, Rio de Janeiro, RJ, Brazil 2. Experimentelle Physik VII and R?ntgen Research Center for Complex Material Systems (RCCM), Universit?t Würzburg, Am Hubland, 97074, Würzburg, Germany 4. Institut für Organische Chemie, Universit?t Würzburg, Am Hubland, 97074, Würzburg, Germany 3. Gemeinschaftslabor für Nanoanalytik, KIT—Karlsruher Institut für Technologie, 76021, Karlsruhe, Germany
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Abstract: | The frontier orbital energies of four different functionalized perylene bisimide derivatives, PBI-Ph(iPr)2, PBI-H4, PBI-F2 and PBI-Cl4, were directly determined by UV-photo electron spectroscopy (UPS) and inverse photo electron spectroscopy (IPES) and are compared to the results from cyclic voltammetry (CV) and optical absorption spectroscopy (UV/VIS). The optical spectra reveal significant differences between monomeric species in solution and assembled molecules in the condensed state for the nearly planar PBI-H4 and PBI-F2, which are attributed to significant π–π stacking interactions in the condensed phase. In contrast, for PBIs with bulky substituents or twisted core, i.e. 2,6-isopropylphenyl substituents at the imide positions (PBI-Ph(iPr)2) or four chlorine substituents at perylene bay positions (PBI-Cl4), similar spectra are observed in solution and in the condensed state, which suggests the absence of strong intermolecular π–π stacking interactions. An entirely different result is obtained for the HOMO/LUMO energy values obtained from UPS/IPES and CV measurements which do not reveal a significant impact of intermolecular π–π stacking interactions. When comparing CV and UPS/IPES results, an accentuated deviation was observed for the perylene bisimide derivatives as compared to correlations found in the literature. |
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