Self‐Assembly of Pseudo[1]rotaxanes by Palladium(II)/Platinum(II)‐Directed Integrative Social Self‐Sorting: Is the Metal Required?

New results are presented on the multicomponent supramolecular synthesis of pseudo[1]rotaxanes, achieved by designing pairs of structurally matching N‐monoalkyl‐4,4'‐bipyridinium/2,7‐diazapyrenium‐based ligands having complementary π‐donor/acceptor features, and intended to self‐assemble into the targeted supramolecules by following integrative self‐sorting processes. In all the studied cases, it was found that the envisioned species, characterized by NMR spectroscopy and MS spectrometry, arise as the main products of the self‐assembly in aqueous media by using palladium(II)/platinum(II) metal centers as the guiding force. Crucially, we have also found that by improving the π‐donor/acceptor properties of the matching pairs of ligands (L4 and L5), the integrative self‐sorting processes prevail even in the absence of metallic ions to afford the heterodimeric species with an association constant being 756±43 M−1. [ABSTRACT FROM AUTHOR]