Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State
Research output: Contribution to journal › Article › Scientific › peer-review
|Number of pages||7|
|Publication status||Published - 14 Jun 2016|
|Publication type||A1 Journal article-refereed|
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.