Elucidating the mechanisms of acidochromic spiropyran-merocyanine interconversion

James T.C. Wojtyk, Adnaan Wasey, Ning Ning Xiao, Peter M. Kazmaier, Shmaryahu Hoz, Chen Yu, Robert P. Lemieux, Erwin Buncel

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The thermal and photochemical processes associated with the acid-induced conversions of 6-nitroBIPS, SP-1, to form the protonated merocyanine (MC-OH +) were investigated via UV/vis spectrophotometric studies in acetone. It was found that the mechanism of trifluoroacetic acid (TFA)-induced ring-opening of the SP and the rate of MC-OH+ formation follows a general acid catalysis mechanism. In accord with this mechanism, the thermal growth of the acid-induced ring-opened form (MC-OH+) was retarded as the concentration of TFA in the medium was increased. The N-protonated SP, i.e., SP-NH+, is formed in a competing side-equilibrium process as an unreactive "sink", with the nitrogen lone-pair no longer available to drive the ring-opening process and resulting in the inverse rate dependence as a linear 1/kobs vs [HA] plot. Addition of a tertiary amine to MC-OH+ regenerated MC which underwent thermal ring closure to the SP, thus restoring its function as a molecular switch. NMR titration of SP samples showed a downfield shift of the N-substituent peak upon increasing the TFA concentration. However, a saturation behavior could not be observed, with SP-1 up to l M acid, unlike the model compound, N,N-dimethylaniline (N,N-DMA), which indicates a base strength order of N,N-DMA > SP-1. Further, we have demonstrated that in solvent acetone, on acidification, the normal photo- and thermochromic behavior is reversed; now MC-OH+ is photochemically transformed into SP-H+, which undergoes thermal ring-opening to MC-OH+.

Original languageEnglish
Pages (from-to)2511-2516
Number of pages6
JournalJournal of Physical Chemistry A
Issue number13
StatePublished - 5 Apr 2007


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