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Analysis of metal ions is critical for chemical monitoring, environmental and clinical applications [1]. For lab-on-achip technologies each circumstance can necessitate the use of different analysis techniques. We therefore developed a more universal platform based a novel spiropyran-conducting polymer (pBSP7) complex that takes advantage of both base chemistries to act as a dual control stimuli responsive material. We utilize this material for the first time to integrate a common chip architecture with multiple analytical techniques to examine the photochemical and electrochemical and sensing of species in solution.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and tempo

Analysis of metal ions is critical for chemical monitoring, environmental and clinical applications [1]. For lab-on-achip technologies each circumstance can necessitate the use of different analysis techniques. We therefore developed a more universal platform based a novel spiropyran-conducting polymer (pBSP7) complex that takes advantage of both base chemistries to act as a dual control stimuli responsive material. We utilize this material for the first time to integrate a common chip architecture with multiple analytical techniques to examine the photochemical and electrochemical and sensing of species in solution.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and tempo

We report the first example of a conducting polymer with a merocyanine incorporated into the polymer backbone by electropolymerisation of a spiropyran moiety covalently linked between two alkoxythiophene units. Utilising the known metal coordination capabilities of merocyanines, introduction of cobalt ions into the electropolymerisation led to an enhancement of the conductivity, morphology and optical properties of the polymer films.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of new applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example in response light and/or electrochemical stimuli; this capability is important in the field of bionics, wherein remote control of the properties of materials opens new possibilities. For example, the ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between surface host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalized with a spiropyran photoswitch (pTTh-SP) and the second with a non photoswitchable methyl acetate moeity (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC was significantly smaller (0.49 ± 0.06 nN) than both the pTTh MA and pTTh-SP. These results suggest that hydrophobic forces are predominant indetermining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and temporal control of the surface binding behaviour of certain proteins with these functionalised surfaces through photoactivation/ deactivation, which, in principle, should facilitate patterned growth behaviour (e.g. using masks or directional illumi

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of new applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example in response light and/or electrochemical stimuli; this capability is important in the field of bionics, wherein remote control of the properties of materials opens new possibilities. For example, the ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between surface host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalized with a spiropyran photoswitch (pTTh-SP) and the second with a non photoswitchable methyl acetate moeity (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC was significantly smaller (0.49 ± 0.06 nN) than both the pTTh MA and pTTh-SP. These results suggest that hydrophobic forces are predominant indetermining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and temporal control of the surface binding behaviour of certain proteins with these functionalised surfaces through photoactivation/ deactivation, which, in principle, should facilitate patterned growth behaviour (e.g. using masks or directional illumi

The aim of this thesis is to understand the basic physico/chemical behaviour of novel nitrospiropyran-substituted-(poly)terthiophene materials. Attractive characteristics that distinguish these materials include electrochemical/photochemical-switching processes. Understanding the fundamental behaviour of these new derivatives is the key to taking advantage of these characteristics. The stimuli induced isomerisation between the colourless spiropyran and the highly coloured merocyanine is the key-process studied in this research. Chapter 2 reports the electrochromic behaviour of spiropyran, through irreversible electrooxidative isomerisation in at least two merocyanine isomers. The molecular photophysical processes of the electrochemically-generated polymer are reported and the properties studied. In Chapter 3 a new monomer, which differs by a single methylene group in the linking ester-linker functionality from the previous one, will be introduced. A nitrospiropyran was used as a reference, and a detailed spectroscopy analysis will help in the description of the thermodynamic properties. Chapter 4 highlights how the polymeric molecular switches can bind an important extracellular protein, fibronectin, and explores by means of microscopy the on-demand tuning of the protein adhesion. A new derivative is presented in Chapter 5, wherein a spiropyran moiety is intercalated between two thiophenes. The electrochemical and optical switching of the spiropyran and thiophene groups were investigated. In Chapter 6 three new spiropyran-based derivatives are presented, and routes to multi-modal switching behavior are explored via photochemical, electrochemical and chemical stimuli, such as pH. Their reversibility and their properties are investigated using both spectroscopic and electroanalytical methods. The final chapter outlines future work and initial progress related to the integration of spiropyran-thiophene polymers into photo-electro active portable analytical devices.

The aim of this thesis is to understand the basic physico/chemical behaviour of novel nitrospiropyran-substituted-(poly)terthiophene materials. Attractive characteristics that distinguish these materials include electrochemical/photochemical-switching processes. Understanding the fundamental behaviour of these new derivatives is the key to taking advantage of these characteristics. The stimuli induced isomerisation between the colourless spiropyran and the highly coloured merocyanine is the key-process studied in this research. Chapter 2 reports the electrochromic behaviour of spiropyran, through irreversible electrooxidative isomerisation in at least two merocyanine isomers. The molecular photophysical processes of the electrochemically-generated polymer are reported and the properties studied. In Chapter 3 a new monomer, which differs by a single methylene group in the linking ester-linker functionality from the previous one, will be introduced. A nitrospiropyran was used as a reference, and a detailed spectroscopy analysis will help in the description of the thermodynamic properties. Chapter 4 highlights how the polymeric molecular switches can bind an important extracellular protein, fibronectin, and explores by means of microscopy the on-demand tuning of the protein adhesion. A new derivative is presented in Chapter 5, wherein a spiropyran moiety is intercalated between two thiophenes. The electrochemical and optical switching of the spiropyran and thiophene groups were investigated. In Chapter 6 three new spiropyran-based derivatives are presented, and routes to multi-modal switching behavior are explored via photochemical, electrochemical and chemical stimuli, such as pH. Their reversibility and their properties are investigated using both spectroscopic and electroanalytical methods. The final chapter outlines future work and initial progress related to the integration of spiropyran-thiophene polymers into photo-electro active portable analytical devices.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and tempo

Analysis of metal ions is critical for chemical monitoring, environmental and clinical applications [1]. For lab-on-achip technologies each circumstance can necessitate the use of different analysis techniques. We therefore developed a more universal platform based a novel spiropyran-conducting polymer (pBSP7) complex that takes advantage of both base chemistries to act as a dual control stimuli responsive material. We utilize this material for the first time to integrate a common chip architecture with multiple analytical techniques to examine the photochemical and electrochemical and sensing of species in solution.

We report the first example of a conducting polymer with a merocyanine incorporated into the polymer backbone by electropolymerisation of a spiropyran moiety covalently linked between two alkoxythiophene units. Utilising the known metal coordination capabilities of merocyanines, introduction of cobalt ions into the electropolymerisation led to an enhancement of the conductivity, morphology and optical properties of the polymer films.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and tempo

Analysis of metal ions is critical for chemical monitoring, environmental and clinical applications [1]. For lab-on-achip technologies each circumstance can necessitate the use of different analysis techniques. We therefore developed a more universal platform based a novel spiropyran-conducting polymer (pBSP7) complex that takes advantage of both base chemistries to act as a dual control stimuli responsive material. We utilize this material for the first time to integrate a common chip architecture with multiple analytical techniques to examine the photochemical and electrochemical and sensing of species in solution.

We report the first example of a conducting polymer with a merocyanine incorporated into the polymer backbone by electropolymerisation of a spiropyran moiety covalently linked between two alkoxythiophene units. Utilising the known metal coordination capabilities of merocyanines, introduction of cobalt ions into the electropolymerisation led to an enhancement of the conductivity, morphology and optical properties of the polymer films.

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and tempo

The aim of this thesis is to understand the basic physico/chemical behaviour of novel nitrospiropyran-substituted-(poly)terthiophene materials. Attractive characteristics that distinguish these materials include electrochemical/photochemical-switching processes. Understanding the fundamental behaviour of these new derivatives is the key to taking advantage of these characteristics. The stimuli induced isomerisation between the colourless spiropyran and the highly coloured merocyanine is the key-process studied in this research. Chapter 2 reports the electrochromic behaviour of spiropyran, through irreversible electrooxidative isomerisation in at least two merocyanine isomers. The molecular photophysical processes of the electrochemically-generated polymer are reported and the properties studied. In Chapter 3 a new monomer, which differs by a single methylene group in the linking ester-linker functionality from the previous one, will be introduced. A nitrospiropyran was used as a reference, and a detailed spectroscopy analysis will help in the description of the thermodynamic properties. Chapter 4 highlights how the polymeric molecular switches can bind an important extracellular protein, fibronectin, and explores by means of microscopy the on-demand tuning of the protein adhesion. A new derivative is presented in Chapter 5, wherein a spiropyran moiety is intercalated between two thiophenes. The electrochemical and optical switching of the spiropyran and thiophene groups were investigated. In Chapter 6 three new spiropyran-based derivatives are presented, and routes to multi-modal switching behavior are explored via photochemical, electrochemical and chemical stimuli, such as pH. Their reversibility and their properties are investigated using both spectroscopic and electroanalytical methods. The final chapter outlines future work and initial progress related to the integration of spiropyran-thiophene polymers into photo-electro active portable analytical devices.

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, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (DSzMC-2 = 43.38 J K-1 mol-1, DSzMC-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''-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, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (DSzMC-2 = 43.38 J K-1 mol-1, DSzMC-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''-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, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (DSzMC-2 = 43.38 J K-1 mol-1, DSzMC-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’’-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.

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.

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.

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, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (DSzMC-2 = 43.38 J K-1 mol-1, DSzMC-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''-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, Ea(MC-3) = 100.39 kJ mol-1) and entropies of activation (DSzMC-2 = 43.38 J K-1 mol-1, DSzMC-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.