title: Kinetic control over pathway complexity in supramolecular polymerization through modulating the energy landscape by rational molecular design.
abstract: 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.
authors.affiliation: Organic Materials Group, Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan).
authors.forename: Soichiro
authors.initials: S
authors.lastname: Ogi
authors.forename: Tomoya
authors.initials: T
authors.lastname: Fukui
authors.forename: Melinda L
authors.initials: ML
authors.lastname: Jue
authors.forename: Masayuki
authors.initials: M
authors.lastname: Takeuchi
authors.forename: Kazunori
authors.initials: K
authors.lastname: Sugiyasu
mesh_terms: D002942:Circular Dichroism; D003510:Cyclohexanes / Q000737:chemistry; D007700:Kinetics; D046911:Macromolecular Substances / Q000737:chemistry*; D058105:Polymerization; D011166:Porphyrins / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics
chemical_list: D003510:Cyclohexanes; D046911:Macromolecular Substances; D011166:Porphyrins; C521475:methylcyclohexane
keywords: pathway complexity; porphyrins; supramolecular polymerization; systems chemistry; time evolution