Aqueous Self‐Assembly and Cation Selectivity of Cobaltabisdicarbollide Dianionic Dumbbells |
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Authors: | Màrius Tarrés Prof. Clara Viñas Patricia González‐Cardoso Dr. Mikko M. Hänninen Prof. Reijo Sillanpää Vladimír Ďorďovič Dr. Mariusz Uchman Prof. Francesc Teixidor Dr. Pavel Matějíček |
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Affiliation: | 1. Institut de Ciència de Materials de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra (Spain);2. Department of Chemistry, University of Jyv?skyl?, 40014 Jyv?skyl? (Finland);3. Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2 (Czech Republic) |
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Abstract: | The anion [3,3′‐Co(C2B9H11)2]? ([COSAN]?) produces aggregates in water. These aggregates are interpreted to be the result of C?H???H?B interactions. It is possible to generate aggregates even after the incorporation of additional functional groups into the [COSAN]? units. The approach is to join two [COSAN]? anions by a linker that can adapt itself to act as a crown ether. The linker has been chosen to have six oxygen atoms, which is the ideal number for K+ selectivity in crown ethers. The linker binds the alkaline metal ions with different affinities; thus showing a distinct degree of selectivity. The highest affinity is shown towards K+ from a mixture containing Li+, Na+, K+, Rb+ and Cs+; this can be indicative of pseudo‐crown ether performance of the dumbbell. One interesting possibility is that the [COSAN]? anions at the two ends of the linker can act as a hook‐and‐loop fastener to close the ring. This facet is intriguing and deserves further consideration for possible applications. The distinct affinity towards alkaline metal ions is corroborated by solubility studies and isothermal calorimetry thermograms. Furthermore, cryoTEM micrographs, along with light scattering results, reveal the existence of small self‐assemblies and compact nanostructures ranging from spheres to single‐/multi‐layer vesicles in aqueous solutions. The studies reported herein show that these dumbbells can have different appearances, either as molecules or aggregates, in water or lipophilic phases; this offers a distinct model as drug carriers. |
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Keywords: | aggregation cations ion exchange metallacarboranes self‐assembly |
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