Redox‐ and Protonation‐Induced Fluorescence Switch in a New Triphenylamine with Six Stable Active or Non‐Active Forms

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

doi:10.1002/chem.201404622

Cited by 55 publications

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References 83 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%

“…[16] The presenceo fF e 3 + as an oxidant renders 1-3 as off-on redox-fluorescent switches. [17][18][19][20][21][22][23][24] Intrinsic to the pyrazoline (fluorophore) there is also ah ighly emissive internal charge transfer (ICT) excited state, whicha th igh proton concentrations results in fluorescenceq uenching due to protonation of the N2 nitrogen atom (receptor). [25,26] Indeed, our proof-of-concepte xamples 1-3 are endowed with two fluorescence sensing mechanisms.…”

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

et al. 2017

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“…29 In vitro cell experiments Two-photon microscopy. C6 glioma cells were seeded at a density of 5 × 10 3 cells per well in 96-well plates and grown in Dulbecco's Modified Eagle Medium F12, enriched with 10% fetal calf serum (FCS) and antibiotics ( penicillin 50 U ml −1 , streptomycin 50 mg ml −1 ).…”

Section: Electrochemistrymentioning

confidence: 99%

A cyclometallated fluorenyl Ir(iii) complex as a potential sensitiser for two-photon excited photodynamic therapy (2PE-PDT)

et al. 2015

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A new Ir(iii) cyclometallated complex bearing a fluorenyl 5-substituted-1,10-phenanthroline ligand ([Ir(ppy)2()][PF6], ppy = 2-phenylpyridine) is presented which exhibits enhanced triplet oxygen sensing properties. The efficacy of this complex to act as a photosensitiser for altering the morphology of C6 Glioma cells that represent malignant nervous tumours has been evaluated. The increased heavy metal effect and related spin-orbit coupling parameters on the photophysical properties of this complex are evidenced by comparison with Ru(ii) analogues. The complex [Ir(ppy)2()][PF6] is shown to exhibit relatively high two-photon absorption efficiencies for the lowest energy MLCT electronic transitions with two-photon absorption cross sections that range from 50 to 80 Goeppert-Mayer units between 750 to 800 nm. Quantum yields for the complex were measured up to 23% and the Stern-Volmer quenching constant, KSV was determined to be 40 bar(-1) in acetonitrile solution, confirming the high efficiency of the complex as a triplet oxygen sensitiser. Preliminary in vitro experiments with C6 Glioma cells treated with [Ir(ppy)2()][PF6], show that the complex is an efficient sensitizer for triplet oxygen, producing cytotoxic singlet oxygen ((1)O2) by two-photon excitation at 740 nm resulting in photodynamic effects that lead to localised cell damage and death.

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“…Noticeably, the oxidation processes are always accompanied by the changes of absorption and/or emission. For this reason, Alain‐Rizzo et al intensively investigated multiple redox states of triarylamine derivatives, in which the more amine groups were incorporated, the richer emission colors can be displayed upon successive electrochemical oxidations . Besides, triarylamines endow better solubility to their polymers, allowing for solution‐casting of flexible films.…”

Section: Elc Materials and Their Luminescent Switchingmentioning

confidence: 99%

Electroluminochromic Materials and Devices

Sun

Chen

Liang

2016

Adv Funct Materials

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Modulation of luminescent color or intensity by varying external stimuli, such as temperature, light, ion concentration, etc., has received increasing attention recently because of numerous applications such as sensors, bioanalysis, optical imaging and memories. For instance, electrically induced luminescent switching — electroluminochromism (ELC) — is one of the most powerful and promising approaches to implement controllable emission due to its facile and precise operation. Recent years have witnessed significant advances in ELC research in the context of materials development and device optimizations. This feature article reviews the fundamentals and recent progress in this emerging field, focusing on working mechanisms, materials, devices and performance improvements. Perspectives for future ELCs are also outlined.

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Redox‐ and Protonation‐Induced Fluorescence Switch in a New Triphenylamine with Six Stable Active or Non‐Active Forms

Cited by 55 publications

References 83 publications

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

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

A cyclometallated fluorenyl Ir(iii) complex as a potential sensitiser for two-photon excited photodynamic therapy (2PE-PDT)

Electroluminochromic Materials and Devices

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