We unravel the impact of metal coordination and light irradiation on hierarchical self-assembly processes by combined theoretical and experimental results.

Cooperative p-p interactions and H-bonding are frequently exploited in supramolecular polymerization;h owever,c lose scrutiny of their mutual interplay has been largely unexplored. Herein, we compare the self-assembly behavior of aseries of C 2 -a nd 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,h ighlighting the reciprocal impact of H-bonding vs.preorganization on the evolution and final outcome of supramolecular systems.

Kooperative p-p-Wechselwirkungen und Wasserstoffbrückenbindungen werden häufig in supramolekularen Polymerisationen genutzt. Nähere Untersuchungen zu deren Zusammenspiel wurden in der Vergangenheit jedochw eitestgehend vernachlässigt. In dieser Arbeit wird das Aggregationsverhalten einer Reihe von C 2 -u nd C 3 -s ymmetrischen Oligophenylenethinylenen, die sich in der Topologie des Amids (N-oder C-zentriert) unterscheiden, verglichen. Diese geringe strukturelle Veränderung bewirkt drastische Unterschiede in den photophysikalischen und supramolekularen Eigenschaften. Somit wird der gegenseitige Einfluss von Wasserstoffbrückenbindungen und geometrischer Präorganisation auf den Assemblierungsprozess und dessen Endresultat in supramolekularen Systemen hervorgehoben.

The latest advancements in semiempirical Hamiltonians have inspired new confidence for the supramolecular computational predictivity. The advanced accuracy of newly developed semiempirical methods is offered for computations of what can provide a valuable database of molecular tuning recommendations for the synthesis of new supramolecular materials. In this work the very versatile and impactful porphyrin is employed for examination of the first basic chemical tuning factors that may drive specific aggregation motifs. The 1D motifs are examined as a function of peripheral substituent steric bulk. Subsequently, a 1D‐wire versus a 3D‐square motif is investigated as a function of the metal–ligand effect. For the first time, an interesting effect of misprediction of semiempirical computations is encountered for a small class of these aggregates and is briefly examined with a conformational search analysis. These findings encourage further in silico work which is greatly required for diminishing the current discovery bottleneck in supramolecular chemistry.