Self-Sorted, Random, and Block Supramolecular Copolymers via Sequence Controlled, Multicomponent Self-Assembly

Multicomponent
supramolecular copolymerization promises to construct
complex nanostructures with emergent properties. However, even with
two monomeric components, various possible outcomes such as self-sorted
supramolecular homopolymers, a random (statistical) supramolecular
copolymer, an alternate supramolecular copolymer, or a complex supramolecular
block copolymer can occur, determined by their intermolecular interactions
and monomer exchange dynamics and hence structural prediction is extremely
challenging. Herein, we target this challenge and demonstrate unprecedented
two-component sequence controlled supramolecular copolymerization
by manipulating thermodynamic and kinetic routes in the pathway complexity
of self-assembly of the constitutive monomers. Extensive molecular
dynamics simulations provided useful mechanistic insights into the
monomer exchange rates and free energy of interactions between the
monomers that dictate the self-assembly pathway and sequence. The
fluorescent nature of core-substituted naphthalene diimide monomers
has been further utilized to characterize the three sequences via
Structured Illumination Microscopy (SIM).