Synthesis and spectral kinetic study of photoinduced processes of photochromic nitro-substituted indoline and benzothienopyrroline spiropyrans in solutions

Ширинян, Валерий З.; Barachevsky, V. А.; Шимкин, А. А.; Krayushkin, М. М.; Mailian, Arthur K.; Tsyganov, Dmitry V.; Vinter, O. A.; Venidiktova, О. V.

doi:10.1007/s11172-010-0168-2

Cited by 7 publications

(4 citation statements)

References 5 publications

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“…To attain this goal, we decided to focus on the spiro-pyran molecular switch, whose UV-induced form (i.e., merocyanine; MC) is significantly more polar than cis-azobenzene, which should trigger a rapid back-isomerization reaction. Our initial experiments with model compounds confirmed this reasoning: we found that whereas the cis form of a simple azobenzene decayed with a first-order rate constant of k ≈ 0.41 day −1 , the open-ring isomer of the parent spiropyran isomerized with k ≈ 0.13 s −1 (in agreement with previous reports 35 )i.e., over four orders of magnitude faster (see the ESI, section 2 †). Recently, we developed the synthesis of spiropyran-functionalized Au 25 nanoclusters and noted a rapid (within 10 minutes) dark disassembly of UV-generated aggregates of these nanoclusters.…”

Section: Introductionsupporting

confidence: 90%

Controlling the lifetimes of dynamic nanoparticle aggregates by spiropyran functionalization

et al. 2016

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Novel light-responsive nanoparticles were synthesized by decorating the surfaces of gold and silver nanoparticles with a nitrospiropyran molecular photoswitch. Upon exposure to UV light in nonpolar solvents, these nanoparticles self-assembled to afford spherical aggregates, which disassembled rapidly when the UV stimulus was turned off. The sizes of these aggregates depended on the nanoparticle concentration, and their lifetimes could be controlled by adjusting the surface concentration of nitrospiropyran on the nanoparticles. The conformational flexibility of nitrospiropyran, which was altered by modifying the structure of the background ligand, had a profound impact on the self-assembly process. By coating the nanoparticles with a spiropyran lacking the nitro group, a conceptually different self-assembly system, relying on a reversible proton transfer, was realized. The resulting particles spontaneously (in the dark) assembled into aggregates that could be readily disassembled upon exposure to blue light.

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Section: Introductionsupporting

confidence: 90%

Controlling the lifetimes of dynamic nanoparticle aggregates by spiropyran functionalization

et al. 2016

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“…53 In solution, the decay rate of the thermally unstable MC-form depends on the solvent polarity. For example, in polar solvents, the thermal conversion of 1′,3′-dihydro-1′,3′-3′-trimethyl-6-nitrospiro[2H]-1-benzopyran-2′,2′-(2H)-indole] (6-nitro-BIPS) tends to have slower rates than in less polar solvents, (i.e., 4.28 × 10 −5 s −1 in ethanol, 54 compared to 5 × 10 −2 s −1 in toluene 55 ). The rate of decay of the MC-form in the SP-LA SAM in this study is on the same time scale as the relaxation of spiropyran when present in polar solvents.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Characterizing the Photoinduced Switching Process of a Nitrospiropyran Self-Assembled Monolayer Using In Situ Sum Frequency Generation Spectroscopy

et al. 2012

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Sum frequency generation (SFG) vibrational spectroscopy is employed to investigate the reversible, photoinduced spiro→merocyanine isomerization of a self-assembled monolayer, the result of attachment of nitrospiropyran to a gold surface using a dithiolane anchoring group. The attachment of these molecular "alligator clips" to spiropyran molecules provide an easily accessible method to self-assemble a robust monolayer of spiropyran on a gold surface, which allows photoswitching of the spiropyran units. Probing the symmetric and antisymmetric stretching modes of the nitro group allows the determination of the structural orientation of the charged moiety with respect to the surface normal as well as the isomerization rates under photoinduced switching conditions. The photoisomerization of the spiropyran SAM on the gold surface is much faster than the rates of switching spiropyrans in a solid crystalline form, and the rate of thermal relaxation of the opened to closed form in this study is found to be on the same time scale as the relaxation of spiropyran when present in solutions with polar solvents.

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“…10 shows the integrated intensities of the c-BTFO4 and MC emission bands obtained from periodic excitation after UV irradiation. The thermal relaxation lifetime of MC is B5.7 h, much longer than observed in various liquid solvents (B10-1800 s), [63][64][65] due to PMMA hindering photoisomerization. It is important to remember that recording the P1 + P3 film's fluorescence also causes c-BTFO4 to photoisomerize back to o-BTFO4, which slowly reduces the former's emission intensity with repeated sampling.…”

Section: P1 + P3 Pmma Filmmentioning

confidence: 80%

Photochrome-doped organic films for photonic keypad locks and multi-state fluorescence

Ritchie

Vamvounis

Soleimaninejad

et al. 2017

Phys. Chem. Chem. Phys.

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The spectroscopic properties of poly(methyl methacrylate) polymer films doped with two kinds of photochromic molecular switches are investigated. A green-fluorescent sulfonyl diarylethene (P1) is combined with either a non-fluorescent diarylethene (P2) or red-fluorescent spiropyran (P3). Photoswitching between the colorless and colored isomers (P1: o-BTFO4 ↔ c-BTFO4, P2: o-DTE ↔ c-DTE, P3: SP ↔ MC) enables the P1 + P2 and P1 + P3 films to be cycled through three distinct states. From the initial state (o-BTFO4 + o-DTE/SP), irradiation with UV light generates the second state (c-BTFO4 + c-DTE/MC), where c-BTFO4 → c-DTE/MC energy transfer is established. Irradiation with green light then generates the third state (c-BTFO4 + o-DTE/SP), where the energy transfer acceptor is no longer present. Finally, irradiation with blue light regenerates the initial state. For the P1 + P2 film, only one state is fluorescent, with the irradiation inputs required to be entered in the correct order to access this state, acting as a keypad lock. For the P1 + P3 film, the states emit either no fluorescence, red fluorescence, or green fluorescence, all using a common excitation wavelength. Additionally, once the fluorescence is activated with UV light, it undergoes a time-dependent color transition from red to green, due to the pairing of P-type and T-type photochromes. These multi-photochromic systems may be useful for security ink or imaging applications.

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Synthesis and spectral kinetic study of photoinduced processes of photochromic nitro-substituted indoline and benzothienopyrroline spiropyrans in solutions

Cited by 7 publications

References 5 publications

Controlling the lifetimes of dynamic nanoparticle aggregates by spiropyran functionalization

Controlling the lifetimes of dynamic nanoparticle aggregates by spiropyran functionalization

Characterizing the Photoinduced Switching Process of a Nitrospiropyran Self-Assembled Monolayer Using In Situ Sum Frequency Generation Spectroscopy

Photochrome-doped organic films for photonic keypad locks and multi-state fluorescence

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