The Effect of Dispersion on the Structure of Diphenyl Ether Aggregates |
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| Authors: | Fabian Dietrich Dominic Bernhard Mariyam Fatima Dr. Cristóbal Pérez Prof. Dr. Melanie Schnell Prof. Dr. Markus Gerhards |
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| Affiliation: | 1. Fachbereich Chemie and Research Center Optimas, TU Kaiserslautern, Kaiserslautern, Germany;2. Deutsches Elektronen-Synchrotron (DESY), Max-Planck-Institut für Struktur und Dynamik der Materie, Hamburg, Germany;3. Christian-Albrechts-Universit?t zu Kiel, Institut für Physikalische Chemie, Kiel, Germany |
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| Abstract: | Dispersion interactions can play an important role in understanding unusual binding behaviors. This is illustrated by a systematic study of the structural preferences of diphenyl ether (DPE)–alcohol aggregates, for which OH???O‐bound or OH???π‐bound isomers can be formed. The investigation was performed through a multi‐spectroscopic approach including IR/UV and microwave methods, combined with a detailed theoretical analysis. The resulting solvent‐size‐dependent trend for the structural preference turns out to be counter‐intuitive: the hydrogen‐bonded OH???O structures become more stable for larger alcohols, which are expected to be stronger dispersion energy donors and thus should prefer an OH???π arrangement. Dispersion interactions in combination with the twisting of the ether upon solvent aggregation are key for understanding this preference. |
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| Keywords: | dispersion molecular complexes non-covalent interactions rotational spectroscopy vibrational spectroscopy |
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