Enhancing the Stability of Photogenerated Benzophenone Triplet Radical Pairs through Supramolecular Assembly
Autor: | Corey R. Martin, Linda S. Shimizu, Martina De Vetta, Baillie A. DeHaven, Ammon J. Sindt, Leticia González, Niklas Noll, Dustin W. Goodlett, Mark D. Smith |
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Rok vydání: | 2018 |
Předmět: |
Quantitative Biology::Biomolecules
Absorption spectroscopy Radical Supramolecular chemistry 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Supramolecular assembly chemistry.chemical_compound Colloid and Surface Chemistry chemistry Benzophenone Molecule Density functional theory Physics::Chemical Physics Solvent effects 0210 nano-technology |
Zdroj: | Journal of the American Chemical Society |
ISSN: | 1520-5126 0002-7863 |
Popis: | Supramolecular assembly of urea-tethered benzophenone molecules results in the formation of remarkably persistent triplet radical pairs upon UV irradiation at room temperature, whereas no radicals were observed in solution. The factors that lead to emergent organic radicals are correlated with the microenvironment around the benzophenone carbonyl, types of proximal hydrogens, and the rigid supramolecular network. The absorption spectra of the linear analogues were rationalized using time-dependent density functional theory calculations on the crystal structure and in dimethyl sulfoxide, employing an implicit solvation model to describe structural and electronic solvent effects. Inspection of the natural transition orbitals for the more important excitation bands of the absorption spectra indicates that crystallization of the benzophenone-containing molecules should present a stark contrast in photophysical properties versus that in solution, which was indeed reflected by their quantum efficiencies upon solid-state assembly. Persistent organic radicals have prospective applications ranging from organic light-emitting diode technology to NMR polarizing agents. |
Databáze: | OpenAIRE |
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