Visible to near-IR molecular switches based on photochromic indoline spiropyrans with a conjugated cationic fragment

Photochromic molecules which can absorb and emit light within the biological window (650-1450 nm) are of great interest for using in various important biomedical applications such as bio-imaging, photopharmacology, targeted drug delivery, etc. Here we present three new indoline spiropyrans containing conjugated cationic fragments and halogen substituents in the 2H-chromene moiety which were synthesized by a simple one-pot method. The molecular structure of the obtained compounds was confirmed by IT-IR, H-1 and C-13 NMR spectroscopy (including 2D methods), HRMS, elemental and single crystal X-ray analysis. Photochemical studies revealed the photochromicactivity of spiropyrans at room temperature which caused photoswitchable fluorescence in the near-IR region after UV-irradiation. While the spirocyclic forms of compounds demonstrated absorption bands in the UV-Vis spectra with maxima in the visible region at about 445 nm and were not fluorescent, the photogenerated merocyanine isomers absorbed in the near-IR range at 708-738 nm and emitted at 768-791 nm. It was found that compound la with fluorine substituent possesses the most red-shifted absorption and emission bands of merocyanine form among all the known photochromic spiropyrans with maxima at 738 and 791 nm correspondingly. TD DFT calculations have shown that the longest wavelength absorption maxima of the merocyanine forms correspond to S-0-S-1 transitions of the isomers with at least one trans-trans-trans-configured vinyl indolium fragment which brings them doser to cya nine-like structure and causes an appearance of the absorption and emission bands in the near-IR region. (C) 2020 Elsevier B.V. All rights reserved.