Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers

Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report an unsymmetrically substituted amphiphilic PtII complex 1 that shows unique self‐assembly behavior in nonpolar media, providing two competing anti‐co...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 58; no. 33; pp. 11344 - 11349
Main Authors Herkert, Lorena, Droste, Jörn, Kartha, Kalathil K., Korevaar, Peter A., de Greef, Tom F. A., Hansen, Michael Ryan, Fernández, Gustavo
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 12.08.2019
EditionInternational ed. in English
Subjects
Assemblies
Assembly
Complexity
Cooperative control
cooperativity
Fibers
Functional materials
Immiscibility
Miscibility
Monomers
Morphology
pathway complexity
Polymers
self-assembly
supramolecular polymerization
Supramolecular polymers
Thermodynamic models
π-conjugated systems
self-assembly
pathway complexity
cooperativity
π-conjugated systems
supramolecular polymerization
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Summary:Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report an unsymmetrically substituted amphiphilic PtII 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. 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.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201905064