Journal of Physical Chemistry B, Vol.122, No.24, 6423-6430, 2018
Proton-Stabilized Photochemically Reversible E/Z Isomerization of Spiropyrans
Spiropyrans undergo C-spiro-O bond breaking to their ring-open protonated E-merocyanine form upon protonation and irradiation via an intermediate protonated Z-merocyanine isomer. We show that the extent of acid-induced ring opening is controlled by matching both the concentration and strength of the acid used and with strong acids full ring opening to the Z-merocyanine isomer occurs spontaneously allowing its characterization by H-1 NMR spectroscopy as well as UV/vis spectroscopy, and reversible switching between Z/E-isomerization by irradiation with UV and visible light. Under sufficiently acidic conditions, both E- and Z-isomers are thermally stable. Judicious choice of acid such that its pK(a) lies between that of the E- and Z-merocyanine forms enables thermally stable switching between spiropyran and E-merocyanine forms and hence pH gating between thermally irreversible and reversible photochromic switching.