Solution Self-Assembly of Chalcogen-Bonding Polymer Partners.

Chalcogen bonding is regarded as a form of noncovalent interaction; however, harnessing chalcogen bonds to drive macromolecular self-assembly remains unexplored. Here we report two classes of chalcogen-bonding partner polymers and their unique self-assembly behaviors in THF/H2O solution. Using simple poly(4-vinylphenyl chalcogenide) (P4VCh, Ch = Te or Se) as the donor polymer and poly(ethylene oxide)-block-poly(4-vinylpyridine N-oxide) (PEO-b-P4VO) as the acceptor polymer, they can form donor-acceptor noncovalent complexes and further aggregate into tubular and spherical assemblies through interchain Te···O and Se···O chalcogen-chalcogen interactions. The small distinction in binding affinity of chalcogen bonds can dictate the assembly of different geometries. Moreover, mixing the strong and weak chalcogen-bonding pairs in various ratios can allow us to obtain ergodic phase evolution with tunable dimensionality and morphology.