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Although the participation of preformed ground-state hydrogen-bonded complexes, in which water molecules are in an appropriate position for receiving the proton from the anthocyanin, cannot be excluded, intramolecular proton-transfer rates are known to exceed the 6-7 ps limit. The fact that these compounds are almost exclusively soluble in water or aqueous ethanol or methanol mixtures limits the use of solvatochromic studies to resolve this point. Nonetheless, preliminary results on the solvatochromism of the synthetic anthocyanin 7-hydroxy-4-methylflavylium (HMF) chloride have shown that the solvent-induced stabilization of the ground state (blue shift of the absorption spectrum) of HMF is proportional to the hydrogen bond donating ability of the solvent while the stabilization of the excited state (red shift of the emission spectrum) is correlated with the hydrogen bond accepting capacity of the solvent. This suggests the presence of hydrogen-bonded HMF-water complexes in both the ground and excited states. However, in the ground state, water molecules are predominantly hydrogen-bond donors to HMF, whereas in the excited state water acts predominantly as a hydrogen-bond acceptor. Thus, excitation would require rotational relaxation of the water molecules in the solvation shell of HMF prior to proton transfer.
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