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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| Published in | Angewandte Chemie International Edition Vol. 58; no. 33; pp. 11344 - 11349 |
|---|---|
| Main Authors | , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
Germany
Wiley Subscription Services, Inc
12.08.2019
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| Edition | International ed. in English |
| Subjects | |
| Online Access | Get full text |
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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.
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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| AbstractList | 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. 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 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. 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. 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. |
| Author | Korevaar, Peter A. Kartha, Kalathil K. Herkert, Lorena Fernández, Gustavo Droste, Jörn Hansen, Michael Ryan de Greef, Tom F. A. |
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| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/31119831$$D View this record in MEDLINE/PubMed |
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| Keywords | self-assembly pathway complexity cooperativity π-conjugated systems supramolecular polymerization |
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| Snippet | Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report an... Controlling the nanoscale morphology in assemblies of π-conjugated molecules is key to developing supramolecular functional materials. Here, we report an... Abstract Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report... |
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| SubjectTerms | 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 |
| Title | Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers |
| URI | https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fanie.201905064 https://www.ncbi.nlm.nih.gov/pubmed/31119831 https://www.proquest.com/docview/2268279444/abstract/ https://search.proquest.com/docview/2232106299 |
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