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Excited state intramolecular proton transfer (ESIPT) in dihydroxyphenyl anthracenes

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Abstract

The photochemistry of three 9-(dihydroxyphenyl)anthracenes 6–8 was studied in neat CH3CN and selected organic solvents, to investigate excited state intramolecular proton transfer (ESIPT) from the phenol to the anthracene moiety. In D2O-CH3CN mixtures, the observed deuterium exchange of 6-8 is consistent with water-mediated (formal) ESIPT process from the ortho phenolic OH to the 10’-position of the anthracene ring, giving rise to quinone methide (QM) intermediates 12-14. There is no ESIPT for the corresponding methoxy-substituted compounds. Introduction of an extra hydroxyl group onto the phenol ring at different positions led to a range of deuterium exchange quantum yields (Φ = 0.03 to 0.15). In addition to the anticipated ESIPT process to the 10’-position, in neat CH3CN and other organic solvents, 6 (but not 7 or 8) undergoes a clean photocyclization to give bridged product 19 in quantitative yield. The mechanism of this unique photocyclization may involve a direct ESIPT or a 1,4-hydrogen transfer from the ortho phenolic OH to the 9’-position of the anthracene ring, generating a zwitterion (20) or diradical (21) intermediate, respectively, followed by ring closure. Fluorescence studies of 6 in various solvents show the existence of both local excited and intramolecular charge transfer states whereas only the former was present for 7 and 8, offering a possible rationalization for the photocyclization pathway.

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  1. Department of Chemistry, Box 3065, University of Victoria, Victoria, British Columbia, Canada, V8W 3V6

    Yu-Hsuan Wang & Peter Wan

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  1. Yu-Hsuan Wang
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  2. Peter Wan
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Correspondence to Peter Wan.

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Electronic supplementary information (ESI) available: Experimental details for the syntheses of compounds 9–11; 1H, 13C, 2D COSY, NOESY, HMQC and HMBC NMR spectra of isolated compounds; fluorescence spectra of 6–8 and 10 in various solvents; fluorescence decay profiles. See

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Wang, YH., Wan, P. Excited state intramolecular proton transfer (ESIPT) in dihydroxyphenyl anthracenes. Photochem Photobiol Sci 10, 1934–1944 (2011). https://doi.org/10.1039/c1pp05187c

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