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Physicochemical study of spiropyran-terthiophene derivatives: photochemistry and thermodynamics

Zanoni, Michele and Coleman, Simon and Fraser, Kevin J. and Byrne, Robert and Wagner, Klaudia and Gambhir, Sanjeev and Officer, David and Wallace, Gordon and Diamond, Dermot (2012) Physicochemical study of spiropyran-terthiophene derivatives: photochemistry and thermodynamics. Physical Chemistry Chemical Physics, 14 . pp. 9112-9120. ISSN 1463-9076

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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-3’-acetate (BSP-2) and 1-(3,3’’-dimethylindoline-6’-nitrobenzospiropyranyl)-2-10 ethyl 4,4’’-didecyloxy-2,2’:5’,2’’-terthiophene-3’-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 cetonitrile, and compared to the parent, non-TThfunctionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and 15 BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (Ea(MC-2) = 75.05 KJ mol-1, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (S‡ MC-2 = - 43.38 J K-1 mol-1, S‡ 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 20 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.

Item Type:Article (Published)
Subjects:Physical Sciences > Analytical chemistry
Physical Sciences > Photochemistry
Physical Sciences > Spectrum analysis
Physical Sciences > Organic chemistry
Physical Sciences > Chemistry
DCU Faculties and Centres:DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences
Research Initiatives and Centres > CLARITY: The Centre for Sensor Web Technologies
Research Initiatives and Centres > National Centre for Sensor Research (NCSR)
Publisher:Royal Society of Chemistry
Official URL:
Copyright Information:©2012 RSC
Use License:This item is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 3.0 License. View License
ID Code:17136
Deposited On:17 Jul 2012 11:21 by Mr. Michele Zanoni. Last Modified 03 Mar 2017 10:25

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