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Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers
Author(s) -
Herkert Lorena,
Droste Jörn,
Kartha Kalathil K.,
Korevaar Peter A.,
de Greef Tom F. A.,
Hansen Michael Ryan,
Fernández Gustavo
Publication year - 2019
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.201905064
Subject(s) - supramolecular chemistry , amphiphile , monomer , conjugated system , self assembly , nanoscopic scale , polymer , molecule , nanotechnology , chemistry , side chain , small molecule , materials science , copolymer , organic chemistry , biochemistry
Abstract Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report an unsymmetrically substituted amphiphilic Pt II complex 1 that shows unique self‐assembly behavior in nonpolar media, providing two competing anti‐cooperative and cooperative pathways with distinct molecular arrangement (long‐ vs. medium‐slipped, respectively) and nanoscale morphology (discs vs. fibers, respectively). With a thermodynamic model, we unravel the competition between the anti‐cooperative and cooperative pathways: buffering of monomers into small‐sized, anti‐cooperative species affects the formation of elongated assemblies, which might open up new strategies for pathway control in self‐assembly. Our findings reveal that side‐chain immiscibility is an efficient method to control anti‐cooperative assemblies and pathway complexity in general.