A macrocyclic benzo-15-crown-5 ether unit tethered to a photochromic naphthopyran by a styryl spacer (MEN) is shown to form a 1:1 complex with magnesium(II). The structure and dynamics of the specific host-metal interactions were investigated by PFG-NMR analysis. A combination of UV/Vis and variable temperature multi-dimensional (1)H NMR photokinetic analysis of the crown-containing styryl naphthopyran and its metal complex was used to probe the effect of metal complexation on the photochromism.

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