Fundamental studies on Brooker's merocyanine

The spectroscopic properties of solvent soluble derivatives of Brooker's simple merocyanine 4-[(1-methyl-4(1H)-pyridinylidene)ethylidene]-2,5-cyclohexadien-1-one, which can in principle exist in two distinct canonical forms, have been assessed both experimentally and theoretically using molecular orbital methods. H-1 and C-13 NMR evidence in a range of solvents suggests that the merocyanine exists as a resonance hybrid which is weighted toward the zwitterion even in solvents of low dielectric constants. In protic solvents, the large hypsochromic shift observed for the merocyanine in the visible region arises from both a dielectric effect and a hydrogen bonding effect. Theoretically, the PM3/COSMO method gives a reasonable account of the structure and spectroscopic shifts of the merocyanine in aprotic solvents, ?The large shifts observed arise because solvents with large dielectric constants have a much greater stabilizing effect on the more polar ground state of the merocyanine than they do on the first excited state. While the same method predicts stable hydrogen-bonded structures for a dihydrate and hexahydrate, it is unable to reproduce the known hypsochromic shift for these solvated species, In contrast, a version of the CNDO/S method does predict the correct trends on hydration though the magnitude of the effect is less than that found experimentally.