Excited-State Aromatic Interactions in the Aggregation-Induced Emission of Molecular Rotors
Autor: | Jiri Sturala, Heather F. Higginbotham, Andrew P. Monkman, Elizabeth H. C. Bromley, Alyssa-Jennifer Avestro, Paul R. McGonigal, Aisha N. Bismillah, William Trewby, Marc K. Etherington, Juan A. Aguilar |
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Rok vydání: | 2017 |
Předmět: |
Range (particle radiation)
Photoluminescence Chemistry Dimer Intermolecular force F100 F200 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Biochemistry Fluorescence Catalysis 3. Good health 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Excited state Intramolecular force 0210 nano-technology Luminescence |
Zdroj: | Journal of the American Chemical Society |
ISSN: | 1520-5126 0002-7863 |
Popis: | Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aromatic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors. |
Databáze: | OpenAIRE |
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