Project summary:

The size of anionic boron clusters is within nano-range, which differentiates them from classical inorganic anions. During the last decade, we have been extensively studying solution behavior of cobalt bis(dicarbollide) anion, COSAN, its derivatives and other anionic boron cluster compounds such as decaborate and dodecaborate dianions. The important aspect is their interaction with macromolecules.(1) Especially, the interaction of metallacarboranes with neutral hydrophilic polymers is almost unparalleled and it leads to unique hybrid nanostructures.(2) To answer our research questions, we will employ a combination of experiment, advanced computer simulations and quantum chemistry calculations. It is clearly evident that behavior of nanometer-sized anionic boron clusters cannot be described by paradigms established for classical ions, and such ions can be taken as unique building blocks in nanochemistry.

In this STARS project, well-defined multi-block copolymers or terpolymers will be synthesized in a way that one block can co-assemble with nano-ion, while the other will stabilize the hybrid nanostructure against the collapse. Another, unique approach will be the synthesis of polymers and copolymers with covalently attached anionic boron cluster compounds to the backbone.(3) All the nanostructures will be studied in respect to potential applications in BNCT, ion-conducting batteries, or advanced nanomaterials research.

At least basic skills in experimental nanochemistry and polymer synthesis are required.

(1)  Jianwei Li, Janouskova O., Fernandez-Alvarez R., Mesikova S., Tosner Z., Kereiche S., Uchman M., Matejicek P.: Designed boron-rich polymeric nanoparticles based on nanoion pairing for boron delivery. Chemistry-A European Journal 2020, 26, 14283–14989; (2) Brus J., Zhigunov A., Czernek J., Kobera L., Uchman M., Matejicek P.: Control over the self-assembly and dynamics of metallacarborane nanorotors by the nature of the polymer matrix: a solid-state NMR study. Macromolecules 2014, 47, 6343–6354; (3) Jianwei Li, Fernandez-Alvarez R., Tosner Z., Kozlik P., Stepanek M., Zhigunov A., Urbanova M., Brus J., Uchman M., Matejicek, P.: Polyelectrolyte based on Polynorbornene with Covalently Attached Metallacarboranes: Synthesis, Characterization and Lithium-Ion Mobility. Macromolecules 2021, 54, 6867-6877.

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