Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers. Issue 33 (4th July 2019)

• Record Type: Journal Article
• Authors: Herkert, Lorena; Droste, Jörn; Kartha, Kalathil K.; Korevaar, Peter A.; de Greef, Tom F. A.; Hansen, Michael Ryan; Fernández, Gustavo
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 33(2019)
• Page Start: 11344
• Page End: 11349
• Publication Date: 2019-07-04
• Subjects: cooperativity -- pathway complexity -- self-assembly -- supramolecular polymerization -- π-conjugated systems; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201905064
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Side‐chain immiscibility allows full control over the formation of a highly stable, discrete anti‐cooperative assembly that is in competition with the formation of cooperative supramolecular polymers, which may open up new strategies for pathway control in self‐assembly.