Abstract Semiempirical molecular orbital calculations have been performed to study the mechanism by which water molecules attack the highly negative oxycyclic oxygen atom of Brooker’s merocyanine 1-methyl-4-(4′-oxidostyryl)pyridinium betaine, M, to form mono-, di-, and tri-hydrated merocyanine complexes. In the case of mono- and di-hydrated complexes, one or two water molecules attack the oxygen atom, respectively, but in the case of the tri-hydrated complex, only two water molecules attack the oxygen atom of M with sp2 hybridization, while the third one forms a H-bond with either one of the oxygen atoms of the coordinated water molecules. The effect of H-bond formation on the molecular and electronic structures of merocyanine is investigated using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory. The calculations show that the hydrated complexes are shifted towards the benzenoid valence structures in the ground state, but shifted towards quinonoid ones upon excitation. On the basis of the calculated charge distribution over the whole skeleton of the complexes, it is found that the dipole moments of the complexes are slightly affected by H-bond formation in the ground state, but strongly decrease upon excitation. The formation of hydrated merocyanine complexes are highly exothermic, downhill reactions, which is explained with respect to the stabilization of the HOMO and oxygen lone-pair levels. We believe that the attacking by water with acidic character on the basic site oxygen atom of merocyanine is a kind of acid–base interaction.
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