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Kinetic Control over Pathway Complexity in Supramolecular Polymerization through Modulating the Energy Landscape by Rational Molecular Design
Author(s) -
Ogi Soichiro,
Fukui Tomoya,
Jue Melinda L.,
Takeuchi Masayuki,
Sugiyasu Kazunori
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201407302
Subject(s) - rational design , polymerization , kinetic energy , energy landscape , supramolecular chemistry , kinetic control , control (management) , chemistry , computer science , materials science , nanotechnology , molecule , polymer , physics , catalysis , organic chemistry , biochemistry , artificial intelligence , classical mechanics
Far‐from‐equilibrium thermodynamic systems that are established as a consequence of coupled equilibria are the origin of the complex behavior of biological systems. Therefore, research in supramolecular chemistry has recently been shifting emphasis from a thermodynamic standpoint to a kinetic one; however, control over the complex kinetic processes is still in its infancy. Herein, we report our attempt to control the time evolution of supramolecular assembly in a process in which the supramolecular assembly transforms from a J‐aggregate to an H‐aggregate over time. The transformation proceeds through a delicate interplay of these two aggregation pathways. We have succeeded in modulating the energy landscape of the respective aggregates by a rational molecular design. On the basis of this understanding of the energy landscape, programming of the time evolution was achieved through adjusting the balance between the coupled equilibria.