Photochromism of nitrobenzospiropyran in phosphonium based ionic liquids

Byrne, Robert; Coleman, Simon; Fraser, Kevin J.; Răduţă, Ana Maria; MacFarlane, Douglas R.; Diamond, Dermot

doi:10.1039/b903772a

Cited by 23 publications

(35 citation statements)

References 42 publications

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“…It was found that the spectroscopic data obtained in phosphonium ILs contradicted what was expected for benzospiropyran in molecular solvents, with the evidence suggesting that the probe molecule was experiencing multiple solvation shells. [23] Within the IL field, phosphonium-based ILs possess some interesting and often advantageous properties. When compared with the popular imidazolium based ILs, phosphonium cations lack the acidic proton which leads to carbene formation, [24] and are often less dense than water when compared to nitrogen based ILs.…”

Section: Introductionmentioning

confidence: 99%

Ionogel-based light-actuated valves for controlling liquid flow in micro-fluidic manifolds

et al. 2010

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We present the fabrication, characterisation and performance of four novel ionic liquid polymer gels (ionogels) as photo-actuated valves incorporated into microfluidic manifolds. The ionogels incorporate benzospiropyran units and phosphonium based ionic liquids. Each ionogel is photo-polymerised in-situ in the channels of a poly(methyl methacrylate) micro-fluidic device, generating a manifold incorporating four different micro-valves. The valves are actuated by simply applying localised white light irradiation, meaning that no physical contact between the actuation impulse (light) and the valve structure is required. Through variation of the composition of the ionogels, each of the micro-valves can be tuned to open at different times under similar illumination conditions. Therefore, flows through the manifold can be independently controlled by a single light source. At present, the contraction process to open the channel is relatively rapid (seconds) while the recovery (expansion) process to re-close the channel is relatively slow (minutes), meaning that the valve, in its current form, is better suited for single-actuation events.

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Section: Introductionmentioning

confidence: 99%

Ionogel-based light-actuated valves for controlling liquid flow in micro-fluidic manifolds

et al. 2010

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“…23 Based on this property, the MC isomer in solution has been studied for its potential use as an empirical indicator of solvent polarity of typical organic solvents 24,25 , aqueous binary solvent mixtures 26 and even ionic liquids. 27,28 Monolayers of spiropyran derivatives have been also bound to glass slides to study the polarity of their microenvironment 29 . Although this approach offers interesting information about the interaction…”

Section: Scheme 1 Photochromic Behaviour Of Monomeric Spiropyransmentioning

confidence: 99%

Spiropyran Polymeric Microcapillary Coatings for Photodetection of Solvent Polarity

et al. 2013

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Fused silica micro-capillaries were functionalised with spiropyran-polymer brushes using surface-initiated ring-opening metathesis polymerisation. Based on the inherited spiropyran properties, the functionalised capillaries were successfully used to photo-identify solvents of different polarity when passing through the micro-capillary in continuous flow. In the present study, six different solvents (toluene, tetrahydrofuran, acetone, acetonitrile, ethanol and methanol) can be easily detected while passing through the modified micro-capillary by simply irradiating a portion of it with UV light (365 nm). This converts the closed spiropyran moiety to the open merocyanine form and as a consequence, the micro-capillary gains a distinct colour and spectral response depending on the polarity of the solvent. The rate of ring opening of the spiropyran-polymer brushes coatings has been determined in-situ in the presence of different 2 solvents, showing that the coloration rate is also influenced by the solvent polarity and therefore can be used as an additional parameter for solvent sensing.

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Section: Introductionmentioning

confidence: 99%

“…16,17,22 Recently, the well-known photo-, thermo-and solvato-chromic properties of benzospiropyran (BSP) and spirooxazine derivatives have been used by our group to provide new insights into the nanostructure of ILs through in situ mediation of their switching behaviour. 16,17 Furthermore the presence of the phenolate anion in the MC isomer provides a weak binding capacity for certain metal ions (d-and f-elements), and the resulting complexes generate new absorbance bands in the visible region, which are directly influenced by the type of metal ion present. [18][19][20][21] Polythiophenes (PThs) are a class of organic polymeric semiconductors with extremely interesting conductivity, electrochromism and electroluminescence 23 properties, which have been explored for applications such as electrochemical sensors and energy harvesting devices.…”

Section: Introductionmentioning

confidence: 99%

Physicochemical study of spiropyran–terthiophene derivatives: photochemistry and thermodynamics

Zanoni

Coleman

Fraser

et al. 2012

Phys. Chem. Chem. Phys.

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The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3''-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4''-didecyloxy-2,2':5',2''-terthiophene-30-acetate (BSP-2) and 1-(3,3''-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4''-didecyloxy-2,2':5',2''-terthiophene-30-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (Ea (MC-2) = 75.05 kJ mol -1 , E a(MC-3) = 100.39 kJ mol -1 ) and entropies of activation (DSz MC-2 = 43.38 J K -1 mol -1 , DSz MC-3 = 37.78 J K -1 mol -1 ) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K -1 mol -1 ) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives. The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3 00 -dimethylindoline-6 0 -nitrobenzospiropyranyl)-2-ethyl 4,4 00 -didecyloxy-2,2 0 :5 0 ,2 00 -terthiophene-3 0 -acetate (BSP-2) and 1-(3,3differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E a(MC-2) = 75.05 kJ mol À1 , E a(MC-3) = 100.39 kJ mol À1 ) and entropies of activation) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K À1 mol À1 ) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.

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Photochromism of nitrobenzospiropyran in phosphonium based ionic liquids

Cited by 23 publications

References 42 publications

Ionogel-based light-actuated valves for controlling liquid flow in micro-fluidic manifolds

Ionogel-based light-actuated valves for controlling liquid flow in micro-fluidic manifolds

Spiropyran Polymeric Microcapillary Coatings for Photodetection of Solvent Polarity

Physicochemical study of spiropyran–terthiophene derivatives: photochemistry and thermodynamics

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