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Fluorescence signaling of aromatic oxoanion inclusion within metal-ion activated molecular receptor complexes formed from 2-(9-anthracenylmethylamino)ethyl-appended cyclen

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Abstract

Our observations that 1-[2-[(9-anthracenylmethylamino)ethyl)-4,7,10-tris[(2S)-2-hydroxy-3-phenoxypropyl]-1,4,7,10-tetraazacyclododecane, L1, complexes Cd(II) to form fluorescent [CdL1]2+ which undergoes a fluorescence change when it acts as an aromatic anion receptor complex has caused us to explore further the potential development of an interesting sequestration/sensor system. Accordingly, three new, octadentate, fluorescent, macrocyclic ligands, 1-[2-[(9-anthracenylmethyl)((2S)-2-hydroxy-3-phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L2), 1-[2-[(9-anthracenyl-methyl)((2S)-2-hydroxy-3-(4′-methyl)phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-(4′-methyl)phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L3), and 1-[2-[(9-anthracenylmethyl)((2S)-2-hydroxy-3-(4′-t-butyl)phenoxypropyl)amino]ethyl]-4,7,10-tris[(2S)-2-hydroxy-3-(4′-t-butyl)phenoxypropyl]-1,4,7,10-tetraazacyclododecane, (L4), have been prepared with a view to using their metal complexes to study aromatic anion sequestration. The eight-coordinate Cd(II) complexes of L2 and L3, [CdL2](ClO4)2·5H2O and [CdL3](ClO4)2·2H2O·2Et2O are both capable of acting as receptors for a range of aromatic oxoanions. This is demonstrated by perturbation of the anthracene derived fluorescence emission intensity as the guest aromatic oxoanion and the receptor complex combine. In 20% aqueous 1,4-dioxane the receptor complex/aromatic oxoanion association constants are in the range of 103.2 M−1 (guest = p-hydroxybenzoate) to 107.3 M−1 (guest = 3,4,5-trihydroxybenzoate).

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Acknowledgment

Funding of this study by the Australian Research Council is gratefully acknowledged.

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Authors and Affiliations

  1. School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA, 5001, Australia

    Adam J. Bradbury & Kevin P. Wainwright

  2. School of Chemistry and Physics, University of Adelaide, Adelaide, SA, 5005, Australia

    Stephen F. Lincoln

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  1. Adam J. Bradbury
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  2. Stephen F. Lincoln
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  3. Kevin P. Wainwright
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Correspondence to Kevin P. Wainwright.

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Bradbury, A.J., Lincoln, S.F. & Wainwright, K.P. Fluorescence signaling of aromatic oxoanion inclusion within metal-ion activated molecular receptor complexes formed from 2-(9-anthracenylmethylamino)ethyl-appended cyclen. J Incl Phenom Macrocycl Chem 71, 567–575 (2011). https://doi.org/10.1007/s10847-011-9924-7

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