Supramolecular polymerization at low monomer concentrations: Enhancing intermolecular interactions and suppressing cyclization by rational molecular design

We present the construction of long-chain water-soluble supramolecular polymers at low monomer concentrations. Naphthalene-based host-enhanced π-π interactions, which possess high binding constants, were used as the driving force of supramolecular polymerization. A monomer, DNDAB, with a rigid, bulky 1,4-diazabicyclo[2.2.2]octane-1,4-diium linker was designed. The design of the monomer structure strongly influenced the efficiency of the supramolecular polymerization. The rigid, bulky linker in DNDAB effectively eliminates cyclization, promoting the formation of long-chain supramolecular polymers at low monomer concentrations. In contrast, a reference monomer containing a flexible linker (DNPDN) only forms oligomers owing to cyclization. Chaining up naphthalene: Long-chain water-soluble supramolecular polymers have been constructed at low monomer concentrations (see scheme). Naphthalene-based host-enhanced π-π interactions are used as the driving force of the supramolecular polymerization and the monomer structure strongly influences the efficiency of the supramolecular polymerization.