Abstract
Cooperative π-π interactions and H-bonding are frequently exploited in supramolecular polymerization; however, close scrutiny of their mutual interplay has been largely unexplored. Herein, we compare the self-assembly behavior of a series of C(2) - and C(3) -symmetrical oligophenyleneethynylenes differing in their amide topology (N- or C-centered). This subtle structural modification brings about drastic changes in their photophysical and supramolecular properties, highlighting the reciprocal impact of H-bonding vs. preorganization on the evolution and final outcome of supramolecular systems.