Designer molecular probes for phosphonium ionic liquids

Byrne, Robert; Coleman, Simon; Gallagher, Simon; Diamond, Dermot

doi:10.1039/b920580b

Cited by 21 publications

(25 citation statements)

References 43 publications

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“…3,5,8–10 The physical and chemical environment significantly changes the photochromic properties, such as switching rates or equilibrium state. 5 In these materials, two types of photochromism have been observed; normal, in which the closed form is observed under dark conditions, and reverse, when the open form is the most stable one.…”

Section: Introductionmentioning

confidence: 99%

Photo-response behavior of electrospun nanofibers based on spiropyran-cyclodextrin modified polymer

Sousa

Guerreiro

et al. 2010

J. Mater. Chem.

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Tunable and durable photochromic materials are a rapidly expanding area of interest, with applications ranging from biomedical devices to industrial-fields. Here we examine electrospun poly (methacrylic acid) PMAA nanofibers covalently modified with the highly photochromic molecule, spiropyran (SP) or a derivate SP which is firstly coupled to a cyclodextrin molecule (βCDSP). The photochromic properties of the starting materials and of the nanofibers were investigated. βCDSP, PMAASP and PMAA-βCDSP polymers exhibited a reverse photochromism. The kinetic results revealed a faster isomerization process for the βCDSP molecule, than that for the PMAA-βCDSP and for the PMAASP, the slowest one. The fastest isomerization is attributed to the presence of a large number of hydroxyl groups of the βCD which stabilizes the merocyanine form via hydrogen bonding, and the slowest isomerization is related to the PMAA chain structure that stabilizes the spiropyran form. Thus, combining the PMAA and βCD properties the photo-isomerization can be modulated. The photoreversibility of this material was verified by UV-visible measurements cycling visible and UV light. Infrared spectroscopy and water contact angle were used for the nanofiber surface characterization, demonstrating the presence of the spiropyran on the mats surface and also showing a minimal effect on nanofiber size and shape when compared to PMAA fiber.

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Section: Introductionmentioning

confidence: 99%

Photo-response behavior of electrospun nanofibers based on spiropyran-cyclodextrin modified polymer

Sousa

Guerreiro

et al. 2010

J. Mater. Chem.

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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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Designer molecular probes for phosphonium ionic liquids

Cited by 21 publications

References 43 publications

Photo-response behavior of electrospun nanofibers based on spiropyran-cyclodextrin modified polymer

Photo-response behavior of electrospun nanofibers based on spiropyran-cyclodextrin modified polymer

Spiropyran Polymeric Microcapillary Coatings for Photodetection of Solvent Polarity

Physicochemical study of spiropyran–terthiophene derivatives: photochemistry and thermodynamics

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