Metallacarborane
clusters, such as COSAN, belong to surface-active
and low-coordinating nanosized anions. Therefore, they have been used
as separate building blocks in self- and co-assembly. As a step forward,
we synthesized via ring-opening metathesis polymerization a novel
polyelectrolyte, poly(norbornene-COSAN), PNC, with metallacarborane
anions covalently attached to a polynorbornene backbone. The resulting
PNC, with the degree of polymerization around 120, is soluble in polar
organic solvents, and it can be deposited on a substrate as separate
polymer chains or as multichain aggregates, with the bundle-of-fibril
patterning. PNC is miscible with polyethylene oxide (PEO), forming
the PNC/PEO composite. As shown by solid-state nuclear magnetic resonance
spectroscopy, Li+ counterions are firmly coordinated in
the PNC matrix, exhibiting rather restricted dynamics. In contrast,
the mixing of PNC with PEO leads to a substantial increase of Li+ dynamics. As the result, the mobility of Li+ in
the PNC/PEO composite remains almost unrestrained, which makes the
COSAN-containing polyelectrolytes promising candidates for ion-conducting
materials.