Check our last paper in ACS Nano

22 September 2014

By using a combination of experimental and theoretical tools, we have elucidated unique physical characteristics of Supramolecular Triarylamine Nanowires (STANWs), their packed structure, as well as the entire kinetics of the associated radical-controlled supramolecular polymerization process. AFM, small angle X-ray scattering, and all-atomic computer modeling reveal the two-columnar `snowflake' internal structure of the fibers involving the π-stacking of triarylamines with alternating handedness. The polymerization process and the kinetics of triarylammonium radicals formation and decay are studied by UV-Vis spectroscopy, nuclear magnetic resonance and electronic paramagnetic resonance. We fully describe these experimental data with theoretical models demonstrating that the supramolecular self-assembly starts by the production of radicals that are required for nucleation of double-columnar fibrils followed by their growth in double-strand filaments. We also elucidate nontrivial kinetics of this self-assembly process revealing sigmoid time dependency and complex self-replicating behavior. The hierarchical approach and other ideas proposed here provide a general tool to study kinetics in a large number of self-assembling fibrillar systems.


Supramolecular Self-Assembly and Radical Kinetics in Conducting Self-Replicating Nanowires
Nyrkova, I ; Moulin, E ; Armao, J.J. ; Maaloum, M ; Heinrich, B ; Rawiso, M ; Niess, F ; Cid, J-J ; Jouault, N ; Buhler, E ; Semenov, A.N. ; Giuseppone, N.
ACS Nano 20148, 10111-10124.