Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

Quinton, Cassandre; Alain-Rizzo, Valérie; Dumas‐Verdes, Cécile; Clavier, Gilles; Miomandre, Fabien; Audebert, Pierre

doi:10.1002/ejoc.201101584

Cited by 48 publications

(51 citation statements)

References 49 publications

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“…At the 5‐position of the pyrazoline ring, 1 – 3 have a ferrocene (electron donor) moiety connected by a methylene spacer (Figure ), which allows for fluorescence switching based on a PET mechanism . The presence of Fe 3+ as an oxidant renders 1 – 3 as off‐on redox‐fluorescent switches . Intrinsic to the pyrazoline (fluorophore) there is also a highly emissive internal charge transfer (ICT) excited state, which at high proton concentrations results in fluorescence quenching due to protonation of the N2 nitrogen atom (receptor) .…”

Section: Figurementioning

confidence: 99%

“…In the case of 5 and 6 protonation of the dimethylaniline receptor results in a covalent bond that ties up the electron lone pairs, whereas in the case of 1 – 3 oxidation by Fe 3+ generates a radical cation, which is a short‐lived intermediate potentially susceptible to a number of competing reaction pathways. Furthermore, it cannot be ruled out that energy transfer between the ferrocenium radical cation and/or Fe 3+ with the pyrazoline provides a deactivation pathway …”

Section: Figurementioning

confidence: 99%

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Redox‐Enabled, pH‐Disabled Pyrazoline–Ferrocene INHIBIT Logic Gates

et al. 2017

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Pyrazoline-ferrocene conjugatesw ith an "electron-donorspacer-fluorophore-receptor" format are demonstrated as redox-fluorescent two-input INHIBIT logic gates.Molecular logic-basedc omputation is now firmly established as am aturing research discipline with researchers contemplating pragmatic uses for this curiosity-based science. [1][2][3][4][5] Medicalrelated innovations such as photodynamic photosensitizers, [6] drug delivery systems [7] and multi-analyte diagnostics [8] are but af ew envisioned applications. One of our visions is the realization of logic gates responsive to the physiochemical parameters of pH and potential( pE), which are fundamental to understanding metal ion solubility in geology and metallurgy as well as in medicine. [9] The development of reliable fluorescentc hemosensors and logic gates for open-shell d-metal ions, particularly Fe 3 + ,r equires overcoming several challenges including issues of solubility.[10] The vast majority of studies in this field continuet ob e reported in organic solvents, where Fe 3 + can form aqua-coordinated speciest hat act as unsuspecting weak acids.[11] Consequently,c omplexation or redox chemistry is often inferred, when matter-of-fact the fluorescent response is due to acidbase chemistry.[12] Furthermore, it is commonly taken for granted that in water Fe 3 + hydrolyses to insoluble Fe(OH) 3 above pH 4. [13] With an understanding of these issues, [10] the applicability of pE-pH logic gates in an applied setting is ar eal possibility.F or example, the detection of Fe 3 + under acidic conditions by fluorescencec ould become ar outine method for the early detection of corrosion of ferrous alloys such as steel. [14] Wu and colleagues have demonstrated an oteworthy logic gate responsive to pH andr edox chemistry.[15] The prototype consisted of ad imethylaniline moiety (protonr eceptor) attached to aP t II complexedt erpyridyl (by av irtual spacer) linked to af errocenyl acetylide (electron donor). From ad esign point of view,t his molecule exemplifies am olecular device with an "electron-donor-fluorophore-spacer-receptor" format. The logic gate exhibited an INHIBIT function with H + and Fe 3 + as the inputs and absorbance at 405 nm as the output. The mechanism of operation involved photoinduced electron transfer (PET) from the dimethylaniline unit and am etal-toligand charget ransfer from the ferrocenyl acetylide. Understandably,b eing ap roof-of-concept, the study wasp erformed in acetonitrile.Herein we now presente xamples of pyrazoline-ferrocene conjugates 1-3 with an ovel "electron-donor-spacer-fluorophore-receptor" format for the first time (Figure 1). In contrast to the example by Wu, we illustrate pE-pH INHIBIT logic gates with an ew structuralc onfiguration (the spaceri sl ocated between the electron donor and fluorophore rather than between the fluorophore and receptor) with fluorescencer ather than absorbance as the output and in 1:1( v/v)m ethanol/water rather than in acetonitrile.At the 5-position of the pyrazoline ring, 1-3 have aferrocene (electro...

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Redox‐Enabled, pH‐Disabled Pyrazoline–Ferrocene INHIBIT Logic Gates

et al. 2017

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“…[68][69][70][71][72][73][74] Recently we showed interest in the study of covalently linked tetrazine-triphenylamine derivatives where the fluorescence of the tetrazine unit could be switched on upon oxidation of the triphenylamine unit. 31,33 However it is interesting to notice, that although these compounds can be regarded in principle as donor-acceptor (D-A) systems, no intramolecular charge transfer (ICT) bands were detected in the UV-vis spectra. In fact, TPA and Tz units have never been covalently combined in a conjugated linked D-A system, in which an ICT band from the donor TPA moiety towards the accepting Tz ring is expected to occur, with the aim of using such an assembly as donor in an OPV cell.…”

Section: Introductionmentioning

confidence: 99%

Triphenylamine/tetrazine based π-conjugated systems as molecular donors for organic solar cells

et al. 2015

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Conjugated systems built by connecting one electron-donor triphenylamine to an electron-withdrawing tetrazine have been prepared using various linkers. We describe here the synthesis, the electrochemical properties and some photophysical properties of these molecules, emphasizing the dependence upon the type of linker between the groups and an organic photovoltaic solar cell was prepared with one derivative.

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“…The low LUMO energy of tetrazine derivatives enables inverse demand Diels-Alder cycloaddition reactions as a heterodiene [1][2][3][4][5][6][7][8][9][10][11][12][13] and stabilizes the anionic intermediate that enables aromatic nucleophilic substitution. [14][15][16][17][18][19] Tetrazine derivatives are also used in coordination chemistry [20][21][22][23][24] because they can form complexes with electron-rich metals. In addition, some tetrazine derivatives show strong electrofluorochromism [25][26][27][28][29][30][31][32] and have been utilized in pollutant detection.…”

Section: Introductionmentioning

confidence: 99%

Novel s-tetrazine-based dyes with enhanced two-photon absorption cross-section

et al. 2015

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This paper reports the synthesis, the linear and non-linear absorption properties of a series of new tetrazine-based D-π-Aπ-D and D-π-A type dyes. In these derivatives, a central tetrazine core was connected with one or two terminal triphenylamine moiety(ies) via various π-conjugated spacers. These compounds were efficiently synthesized by Stille or Suzuki-Miyaura cross coupling as a key step. Their photophysical properties, including one-photon absorption and twophoton absorption (2PA), were investigated with special attention to structure-properties relationships. Large 2PA crosssections (>800 GM) of these tetrazine dyes were evaluated by open aperture z-scan and non-degenerate 2PA techniques. The strong 2PA of these molecules are attributed to the extended π system and to the enhanced intramolecular charge transfer between triphenylamine donor and center tetrazine acceptor.

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Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

Cited by 48 publications

References 49 publications

Redox‐Enabled, pH‐Disabled Pyrazoline–Ferrocene INHIBIT Logic Gates

Redox‐Enabled, pH‐Disabled Pyrazoline–Ferrocene INHIBIT Logic Gates

Triphenylamine/tetrazine based π-conjugated systems as molecular donors for organic solar cells

Novel s-tetrazine-based dyes with enhanced two-photon absorption cross-section

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