Pathway control in cooperative vs. anti-cooperative supramolecular polymers

Lorena Herkert, Jörn Droste, Kalathil K. Kartha, Peter A. Korevaar, Tom F.A. de Greef, Michael Ryan Hansen, Gustavo Fernández (Corresponding author)

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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 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.

Original languageEnglish
Pages (from-to)11344-11349
Number of pages6
JournalAngewandte Chemie - International Edition
Volume58
Issue number33
Early online date22 May 2019
DOIs
Publication statusPublished - 5 Aug 2019

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Keywords

  • cooperativity
  • pathway complexity
  • self-assembly
  • supramolecular polymerization
  • π-conjugated systems
  • pi-conjugated systems

Cite this

Herkert, L., Droste, J., Kartha, K. K., Korevaar, P. A., de Greef, T. F. A., Hansen, M. R., & Fernández, G. (2019). Pathway control in cooperative vs. anti-cooperative supramolecular polymers. Angewandte Chemie - International Edition, 58(33), 11344-11349. https://doi.org/10.1002/anie.201905064