Description:
<jats:title>Abstract</jats:title><jats:p>Macromolecules have a strong tendency to interact with each other in solution to form a supramolecular structure through various secondary binding forces. In this study, nucleobase‐containing templates poly(9‐(4‐vinylbenzyl)adenine) (P<jats:sub>S</jats:sub>AH) and poly(1‐(4‐vinylbenzyl)cytosine) (P<jats:sub>S</jats:sub>CH) are prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Vinylbenzyl thymine (M<jats:sub>S</jats:sub>T) is polymerized in the presence of these two nucleobase‐containing templates. M<jats:sub>S</jats:sub>T shows higher affinities toward the template P<jats:sub>S</jats:sub>AH compared with the template P<jats:sub>S</jats:sub>CH. In accordance with the Watson–Crick pairing principle, thymine forms hydrogen bonding (H‐bonding) with adenine, but not between thymine and cytosine. A complex is formed when P<jats:sub>S</jats:sub>AH is used as template which indicates that there is a template polymerization of nucleobase complexes via molecular recognition.</jats:p>