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 FT-IR, 1H and 13C NMR spectroscopy (including 2D methods), HRMS, elemental and single crystal X-ray analysis. Photochemical studies revealed the photochromic activity 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 1a 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 S0-S1 transitions of the isomers with at least one trans-trans-trans-configured vinylindolium fragment which brings them closer to cyanine-like structure and causes an appearance of the absorption and emission bands in the near-IR region.
Keywords: Fluorescence; Molecular switches; Near-IR; Photochromism; Single crystal X-ray analysis; Spiropyrans; TD DFT calculations.
Copyright © 2020 Elsevier B.V. All rights reserved.