A high fatigue resistant, photoswitchable fluorescent spiropyran–polyoxometalate–BODIPY single-molecule

Saad, Ali; Oms, Olivier; Dolbecq, Anne; Menet, Clotilde; Dessapt, Rémi; Serier‐Brault, Hélène; Allard, Emmanuel; Baczko, Krystyna; Mialane, Pierre

doi:10.1039/c5cc06217a

Cited by 49 publications

(35 citation statements)

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“…[11] Recently, a quenching of the luminescence of the BODIPY fragment in a photochromic spiropyran-polyoxomolybdate-BODIPY complex has been evidenced. [12] But systems -incorporating POM or not -with different emission energies remain largely to be developed. We previously described the synthesis and photochromic properties (both in solution and in the solid state) of a new family of polyoxometalate (POM)-based organic/inorganic hybrids, in which polyoxotungstates are covalently linked to a spiropyran or a benzospiropyran unit.…”

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Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

et al. 2017

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Abstract:The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that (i) both closed and open forms are emissive with distinct spectral features (λem, (closed form) = 530 nm, λem, (open form) = 670 nm); (ii) the fluorescence of the BSPR unit of the POM-based hybrid is considerably enhanced compared to BSPR reference compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), facilitating the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of hybrid give an intimate understanding of the structural conformation adopted by the hybrid and show that the nitro-aryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR.Photo-responsive molecules and materials are currently receiving considerable attention regarding their potentiality for the development of advanced photonic devices in various applications such as information storage, optical switches, protection, smart labelling and super-resolution microscopy. [1] Particularly, the elaboration of molecular systems combining photo-switching and fluorescence properties constitute a promising research field because of the high sensitivity, resolution, contrast and fast response times of the fluorescence. Furthermore, the emergence of single-molecule fluorescence spectroscopy opens the route to high memory density nanodevices, in which a single molecule would work as one bit of memory, [2] and thus strongly supports the molecular approach. Until now, the development of molecular systems displaying photo-modulated emissive properties has mostly relied on the association of luminescent and photochromic components in a molecular assembly. [3] In these systems, the transformation of the photochromic component is exploited to modulate the emission intensity of the luminescent component on the basis of electron and/or energy transfer. [4] However, molecular systems displaying tuneable fluorescence features, i.e. having different emission energies, according to the form of the photochromic unit, have been scarcely reported in the literature. [5] The coexistence of photochromic and fluorescence properties, in a single photoactive unit, is rarely achieved since in case of fast internal conversion only one photophysical property (photochromic vs fluorescence) is observed. Furthermore the ns timescale of fluorescence [6] is considerably slower than the fs to ps timescale of the ring opening/closure dynamics occurring in the photochromic events. [7] POMs are nanosized molecular oxo cluster that are currently receiving considerable attention because of their wide range of properties and their potential applications in various fields such as analytical chemistry, medicine and ...

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confidence: 99%

“…[11] Recently, aquenching of the luminescence of the BODIPY fragment in ap hotochromic spiropyran-polyoxomolybdate-BODIPY complex has been observed. [12] But systems incorporating POM or not with different emission energies remain largely to be developed.…”

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confidence: 99%

Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

et al. 2017

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“…On another hand, spiropyrans constitute an important class of photochromic organic compounds . Recently, a quenching of the luminescence of the BODIPY fragment in a photochromic spiropyran–polyoxomolybdate–BODIPY complex has been observed . But systems incorporating POM or not with different emission energies remain largely to be developed.…”

Section: Figurementioning

confidence: 99%

Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

et al. 2017

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Abstract:The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that (i) both closed and open forms are emissive with distinct spectral features (λem, (closed form) = 530 nm, λem, (open form) = 670 nm); (ii) the fluorescence of the BSPR unit of the POM-based hybrid is considerably enhanced compared to BSPR reference compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), facilitating the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of hybrid give an intimate understanding of the structural conformation adopted by the hybrid and show that the nitro-aryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR.Photo-responsive molecules and materials are currently receiving considerable attention regarding their potentiality for the development of advanced photonic devices in various applications such as information storage, optical switches, protection, smart labelling and super-resolution microscopy.[1] Particularly, the elaboration of molecular systems combining photo-switching and fluorescence properties constitute a promising research field because of the high sensitivity, resolution, contrast and fast response times of the fluorescence. Furthermore, the emergence of single-molecule fluorescence spectroscopy opens the route to high memory density nanodevices, in which a single molecule would work as one bit of memory, [2] and thus strongly supports the molecular approach. Until now, the development of molecular systems displaying photo-modulated emissive properties has mostly relied on the association of luminescent and photochromic components in a molecular assembly. [3] In these systems, the transformation of the photochromic component is exploited to modulate the emission intensity of the luminescent component on the basis of electron and/or energy transfer.[4] However, molecular systems displaying tuneable fluorescence features, i.e. having different emission energies, according to the form of the photochromic unit, have been scarcely reported in the literature.[5] The coexistence of photochromic and fluorescence properties, in a single photoactive unit, is rarely achieved since in case of fast internal conversion only one photophysical property (photochromic vs fluorescence) is observed. Furthermore the ns timescale of fluorescence [6] is considerably slower than the fs to ps timescale of the ring opening/closure dynamics occurring in the photochromic events. [7] POMs are nanosized molecular oxo cluster that are currently receiving considerable attention because of their wide range of properties and their potential applications in various fields such as analytical chemistry, medicine and cat...

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“…[15] SP-POM possesseso ne free amino group, which allows ap ost-functionalization by as econd peptide-coupling reaction as shown recently by the synthesis of ab iphotochromic hybrid POM or ap hotoswitchable fluorescent SP-POM-BODIPY (BODIPY = boron-dipyrromethene) molecule. [16] Following this synthetic pathway, (TBA) 3 [MnMo 6 O 18 {(OCH 2 ) 3 CNHC 21 H 19 N 2 O 4 }{(OCH 2 ) 3 CNHC 16 H 28 O}] (SP-POM-C16) (Scheme 2) has been isolated starting from palmitic acid.…”

Section: Introductionmentioning

confidence: 99%

Light‐ and Solvent‐Controlled Self‐Assembly Behavior of Spiropyran–Polyoxometalate–Alkyl Hybrid Molecules

Chu

Yin

et al. 2016

Chemistry A European J

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A molecular photochromic spiropyran-polyoxometalate-alkyl organic-inorganic hybrid has been synthesized and fully characterized. The reversible switching of the hydrophobic spiropyran fragment to the hydrophilic merocyanine one can be easily achieved under light irradiation at different wavelengths. This switch changes the amphiphilic feature of the hybrid, leading to a light-controlled self-assembly behavior in solution. It has been shown that the hybrid can reversibly self-assemble into vesicles in polar solvents and irreversibly into reverse vesicles in non-polar solvents. The sizes of the vesicles and the reverse vesicles are both tunable by the polarity of the solvent, with the hydrophobic interactions being the main driving force.

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A high fatigue resistant, photoswitchable fluorescent spiropyran–polyoxometalate–BODIPY single-molecule

Abstract: The tuning of the fluorescence through the activation of the photochromic part in an unprecedented covalent spiropyran-polyoxometalate-BODIPY tricomponent points out the high photofatigue resistance of such molecular switches.

Cited by 49 publications

References 61 publications

Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

Photochromism and Dual‐Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

Light‐ and Solvent‐Controlled Self‐Assembly Behavior of Spiropyran–Polyoxometalate–Alkyl Hybrid Molecules

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