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Tytuł:
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Visible to near-IR molecular switches based on photochromic indoline spiropyrans with a conjugated cationic fragment.
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Autorzy:
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Pugachev AD; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Ozhogin IV; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation. Electronic address: .
Lukyanova MB; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Lukyanov BS; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation; Don State Technical University, 1 Gagarin sq., 344000 Rostov-on-Don, Russian Federation.
Rostovtseva IA; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Dorogan IV; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Makarova NI; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Tkachev VV; Institute of Problems of Chemical Physics, Russian Acadeemy of Sciences, 1 Akad. Semenova ave., 142432 Chernogolovka, Moscow Region, Russian Federation; Institute of Physiologically Active Substances, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation.
Metelitsa AV; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka ave., 344090 Rostov-on-Don, Russian Federation.
Aldoshin SM; Institute of Problems of Chemical Physics, Russian Acadeemy of Sciences, 1 Akad. Semenova ave., 142432 Chernogolovka, Moscow Region, Russian Federation.
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Źródło:
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Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy [Spectrochim Acta A Mol Biomol Spectrosc] 2020 Apr 05; Vol. 230, pp. 118041. Date of Electronic Publication: 2020 Jan 07.
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Typ publikacji:
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Journal Article
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Język:
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English
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Imprint Name(s):
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Publication: : Amsterdam : Elsevier
Original Publication: [Kidlington, Oxford, U.K. ; Tarrytown, NY] : Pergamon, c1994-
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Contributed Indexing:
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Keywords: Fluorescence; Molecular switches; Near-IR; Photochromism; Single crystal X-ray analysis; Spiropyrans; TD DFT calculations
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Entry Date(s):
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Date Created: 20200120 Date Completed: 20200219 Latest Revision: 20200219
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Update Code:
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20240104
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DOI:
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10.1016/j.saa.2020.118041
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PMID:
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31955116
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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, 1 H and 13 C 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 S 0 -S 1 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.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2020 Elsevier B.V. All rights reserved.)
