| Autor: |
Wimberger L; School of Chemistry, UNSW Sydney, Sydney, New South Wales 2052, Australia., Prasad SKK; School of Chemistry, UNSW Sydney, Sydney, New South Wales 2052, Australia., Peeks MD; School of Chemistry, UNSW Sydney, Sydney, New South Wales 2052, Australia., Andréasson J; Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Göteborg 412 96, Sweden., Schmidt TW; School of Chemistry, UNSW Sydney, Sydney, New South Wales 2052, Australia., Beves JE; School of Chemistry, UNSW Sydney, Sydney, New South Wales 2052, Australia. |
| Abstrakt: |
Molecular photoswitches capable of generating precise pH changes will allow pH-dependent processes to be controlled remotely and noninvasively with light. We introduce a series of new merocyanine photoswitches, which deliver reversible bulk pH changes up to 3.2 pH units (pH 6.5 to pH 3.3) upon irradiation with 450 nm light, displaying tunable and predictable timescales for thermal recovery. We present models to show that the key parameters for optimizing the bulk pH changes are measurable: the solubility of the photoswitch, the acidity of the merocyanine form, the thermal equilibrium position between the spiropyran and the merocyanine isomers, and the increased acidity under visible light irradiation. Using ultrafast transient absorption spectroscopy, we determined the quantum yields for the ring-closing reaction and found that the lifetimes of the transient cis -merocyanine isomers ranged from 30 to 550 ns. Quantum yields did not appear to be a limitation for bulk pH switching. The models we present use experimentally determined parameters and are, in principle, able to predict the change in pH obtained for any related merocyanine photoacid. |
