Photoswitchable Molecular Systems Based on Spiropyrans and Spirooxazines

Minkin, Vladimir I.

doi:10.1002/9783527634408.ch2

Cited by 40 publications

(23 citation statements)

References 219 publications

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“…[15] Indolino-spiropyrans derivatives, [6] for example, are not only known as photoswitchable molecules but they also demonstrate interesting acidochromic properties. [15b,16] Owing to the structural similarity of our products 2 [8] and 7 with indolinospiropyrans by the presence of a N,O-aminal functional group, we realized that there could possibly be an acidochromic equilibrium that would allow us to observe color changes at different pH (Scheme 3).…”

Section: Acidochromic Studymentioning

confidence: 99%

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Synthesis of 3‐Fluoro‐2‐hetarylindoles and 3,3‐Difluoro‐2‐hetarylindolines through Lewis Acid‐Catalyzed Formation of 3,3‐Difluoroindolium Ions

et al. 2015

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Synthesis of 3-fluoro-2-hetarylindoles through addition of hetarenes to 3,3-difluoroindolium ions generated in situ by Zn(OTf) 2 -catalyzed oxazolidine ring opening is described. Indoles, pyrroles and alkyl-substituted furans can be used as hetaryl nucleophiles to afford a range of 3-fluoro-2-hetarylindole products 6 in 56-95 % yields. A diverse array of 3,3-difluorinated 2-hetarylindolines 7 can also be synthesized in

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Section: Acidochromic Studymentioning

confidence: 99%

“…[3] In addition, these structural motifs are also used in other fields, such as agrochemicals [4] and materials. [5,6] For example, indolino[1, 2-b]oxazolines, [5] indolinospiropyrans, and indolino-spirooxazines, [6] can be used as molecular switches in molecular electronics and photonics, logic gates, and color switching devices.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 3‐Fluoro‐2‐hetarylindoles and 3,3‐Difluoro‐2‐hetarylindolines through Lewis Acid‐Catalyzed Formation of 3,3‐Difluoroindolium Ions

et al. 2015

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“…Spiropyrans and spirooxazines are exemplary photochromic compounds that have gained great attention in the last decades because they allow to reversibly alter and control the physical and chemical properties of functional compounds and materials through the irradiation with light [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. These classes of compounds possess advantageous properties, such as good synthe-tic accessibility, which allows a broad range of structural modifications and high quantum yields of the photoreaction [12,15,16]. The photochromism is based on a reversible electrocyclic reaction that proceeds through the UV light-induced cleavage of the C2'-O bond of the closed, colorless form to give the colored, metastable merocyanine form, whereas the Scheme 1: Photo-or cation-induced ring-opening reaction of spirooxazine 1a SO ; M n+ = Pb 2+ , La 3+ , Eu 3+ , Tb 3+ [17].…”

Section: Introductionmentioning

confidence: 99%

Cation-induced ring-opening and oxidation reaction of photoreluctant spirooxazine–quinolizinium conjugates

Pithan¹,

Ihmels²

2020

Beilstein J. Org. Chem.

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Two new spiroindolinonaphthoxazine derivatives with an electron-accepting styrylquinolizinium or styrylcoralyne unit, respectively, were synthesized, and the influence of such an arylvinyl substituent on the chemical and photochemical properties of the compounds was investigated. Specifically, these spirooxazines turned out to be resistant towards the photoinduced merocyanine formation, and the irradiation with light mainly led to photodegradation of the substrates. However, it was shown by colorimetric and fluorimetric screening assays as well as by detailed NMR spectroscopic and mass spectrometric studies that the addition of particular metal ions (Cu2+, Fe3+, and to a certain extent Hg2+) initially induced a ring-opening reaction that was irreversibly followed by a fast ring closure–deprotonation–oxidation sequence to give styryl-substituted naphthoxazole derivatives as the products quantitatively. For the quinolizinium-substituted spirooxazine derivative, the formation of the respective oxidation product caused the development of a broad absorption band between 425 nm and 500 nm and a new emission band at λfl = 628 nm, so that it may be employed as a selective chemosensor or chemodosimeter for the colorimetric and fluorimetric detection of Cu2+ and Fe3+.

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“…In this context, numerous molecular systems combining different types of switchable moieties have been reported. − If the development of photo- and redox-active materials is particularly attractive for applications in molecular memories or logic gates, − their selective addressability is still quite challenging when several switching units of the same type are present especially when the stimulus is light. For example, numerous systems incorporating several diarylethene (DAE) units, undoubtedly the most studied photoswitch family, − exhibit restricted photochromic performances.…”

Section: Introductionmentioning

confidence: 99%

BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

et al. 2019

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The design of multistate/multifunctional molecular systems arouses a lot of interest. Such compounds are able to commutate between two metastable states by the application of an external stimulation such as light, heat, protons, or electrons. In this context, we are interested in molecular switches based on indolino-oxazolidine (BOX) which is a relatively less-known sub-class of multimodal addressable units. Their particularity consists of the possibility to induce the opening/closing of the oxazolidine ring by using indifferently light, electrochemical, or acido-basic stimulation. Up to now, most of the reported systems based on BOX have allowed to modulate a molecular property but only between two discrete levels which can only be extended by their association with other classical switchable unit such as a dithienylethene unit. For this reason, we report here our effort to enhance the number of metastable states by simply connecting two identical BOX units by a bithiophene (BT) linker. The resulting system's ability to switch between the three possible metastable states was investigated. Irrespective of the nature of the stimulation, full commutation of the system could be reached, but our work mainly revealed that the opening of both oxazolidine rings occurs in a stepwise manner. If this unreported selectivity upon a unique stimulus with two identical switchable units is observed irrespective of the stimulation, it must be pointed out that its efficiency depends on the nature of the latter. The direct stimulation with acid or light leads to the coexistence of the three different states of the system over a broad stimulation period. On the contrary, the indirect stimulation of BOX via an electromediated process due to the electroactivity of BT enhances the selective addressability between both identical BOX units.

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Photoswitchable Molecular Systems Based on Spiropyrans and Spirooxazines

Cited by 40 publications

References 219 publications

Synthesis of 3‐Fluoro‐2‐hetarylindoles and 3,3‐Difluoro‐2‐hetarylindolines through Lewis Acid‐Catalyzed Formation of 3,3‐Difluoroindolium Ions

Synthesis of 3‐Fluoro‐2‐hetarylindoles and 3,3‐Difluoro‐2‐hetarylindolines through Lewis Acid‐Catalyzed Formation of 3,3‐Difluoroindolium Ions

Cation-induced ring-opening and oxidation reaction of photoreluctant spirooxazine–quinolizinium conjugates

BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

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