Three Ways Isolable Carbenes Can Modulate Emission of NH-Containing Fluorophores
| Autor: | Sloane Evariste, Zacharias J. Kinney, Jerod M. Kieser, Joshua R. Gaffen, Arnold L. Rheingold, Alexandra M Harrison, John D. Protasiewicz |
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| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Carbazole Hydrogen bond General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Biochemistry Fluorescence Catalysis 0104 chemical sciences Adduct chemistry.chemical_compound Colloid and Surface Chemistry chemistry Molecule Singlet state Carbene Alkyl |
| Zdroj: | Journal of the American Chemical Society. 141(30) |
| ISSN: | 1520-5126 |
| Popis: | Fluorescent molecules and materials that exhibit emission changes in response to analytes are of great interest across multiple disciplines. Herein, we investigate the response of NH-containing fluorophores carbazole and 2-phenylbenzimidazole (Ph-BIM) with two representative isolable singlet carbenes. Specifically, N-heterocyclic carbene 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and cyclic (alkyl)(amino)carbene (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene (EtCAAC) were discovered to afford three different types of reaction products with carbazole and Ph-BIM. Depending on the reaction pair, hydrogen bonding (1), NH-insertion (2,3), or proton transfer (4) products can be isolated, each displaying variable photophysical responses. These products have been structurally authenticated by single crystal X-ray diffraction and NMR spectrometric methods. Studies of the solution state behavior of 1-4 reveals that these adducts are labile and can reversibly dissociate to free carbenes and fluorophores to varying extents. These equilibria produce concentration dependent solution state behavior as identified and quantified via UV-visible absorption, emission, 1H DOSY, and NMR spectroscopic measurements. |
| Databáze: | OpenAIRE |
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