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Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State

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Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State. / Poutanen, Mikko; Ikkala, Olli; Priimägi, Arri.

In: Macromolecules, Vol. 49, No. 11, 14.06.2016, p. 4095-4101.

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Poutanen, Mikko ; Ikkala, Olli ; Priimägi, Arri. / Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State. In: Macromolecules. 2016 ; Vol. 49, No. 11. pp. 4095-4101.

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@article{3a88c9cab41344149dcc8c5908c2d57b,
title = "Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State",
abstract = "Light-responsive supramolecular self-assemblies exhibit interplay between order and dynamics of the self-assembling motifs, through which the thermal isomerization rate of azobenzene chromophores can be tuned by orders of magnitude. By using supramolecular complexes of 4-(4-alkylphenylazo)phenols hydrogen-bonded to poly(4-vinylpyridine) as model systems, we demonstrate that the thermal isomerization rate of the hydroxyazobenzene derivatives increases 5700-fold when the material undergoes a transformation from a disordered, low-azobenzene-concentration state to a high-concentration state exhibiting lamellar, smectic-like self-assembly. Drastically smaller thermal isomerization rates are observed in disordered structures. This allows us to attribute the change to a combination of increased number density of the hydroxyazobenzenes inducing plasticization, and cooperativity created by the chromophore-chromophore interactions through self-assembled molecular order and alignment. Our results pinpoint the importance of molecular self-assembly and intermolecular interactions in modifying the dynamics in supramolecular complexes in a controlled manner. We foresee this to be important in light-controlled dynamic materials.",
author = "Mikko Poutanen and Olli Ikkala and Arri Priim{\"a}gi",
year = "2016",
month = "6",
day = "14",
doi = "10.1021/acs.macromol.6b00562",
language = "English",
volume = "49",
pages = "4095--4101",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "11",

}

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TY - JOUR

T1 - Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State

AU - Poutanen, Mikko

AU - Ikkala, Olli

AU - Priimägi, Arri

PY - 2016/6/14

Y1 - 2016/6/14

N2 - Light-responsive supramolecular self-assemblies exhibit interplay between order and dynamics of the self-assembling motifs, through which the thermal isomerization rate of azobenzene chromophores can be tuned by orders of magnitude. By using supramolecular complexes of 4-(4-alkylphenylazo)phenols hydrogen-bonded to poly(4-vinylpyridine) as model systems, we demonstrate that the thermal isomerization rate of the hydroxyazobenzene derivatives increases 5700-fold when the material undergoes a transformation from a disordered, low-azobenzene-concentration state to a high-concentration state exhibiting lamellar, smectic-like self-assembly. Drastically smaller thermal isomerization rates are observed in disordered structures. This allows us to attribute the change to a combination of increased number density of the hydroxyazobenzenes inducing plasticization, and cooperativity created by the chromophore-chromophore interactions through self-assembled molecular order and alignment. Our results pinpoint the importance of molecular self-assembly and intermolecular interactions in modifying the dynamics in supramolecular complexes in a controlled manner. We foresee this to be important in light-controlled dynamic materials.

AB - Light-responsive supramolecular self-assemblies exhibit interplay between order and dynamics of the self-assembling motifs, through which the thermal isomerization rate of azobenzene chromophores can be tuned by orders of magnitude. By using supramolecular complexes of 4-(4-alkylphenylazo)phenols hydrogen-bonded to poly(4-vinylpyridine) as model systems, we demonstrate that the thermal isomerization rate of the hydroxyazobenzene derivatives increases 5700-fold when the material undergoes a transformation from a disordered, low-azobenzene-concentration state to a high-concentration state exhibiting lamellar, smectic-like self-assembly. Drastically smaller thermal isomerization rates are observed in disordered structures. This allows us to attribute the change to a combination of increased number density of the hydroxyazobenzenes inducing plasticization, and cooperativity created by the chromophore-chromophore interactions through self-assembled molecular order and alignment. Our results pinpoint the importance of molecular self-assembly and intermolecular interactions in modifying the dynamics in supramolecular complexes in a controlled manner. We foresee this to be important in light-controlled dynamic materials.

U2 - 10.1021/acs.macromol.6b00562

DO - 10.1021/acs.macromol.6b00562

M3 - Article

VL - 49

SP - 4095

EP - 4101

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 11

ER -