Metallomacrocycles That Incorporate Cofacially Aligned Diimide Units

Pyromellitic diimide and naphthalene diimide moieties were incorporated into hemilabile phosphanylalkyl thioether ligands. These ligands reacted with [Cu(CH₃CN)₄]PF₆ and [Rh(NBD)Cl]₂ (NBD=norbornadiene) by the weak‐link approach to form condensed intermediates. Upon reaction of each diimide ligand with these transition‐metal precursors, the two diimide units became cofacially aligned within a supramolecular macrocyclic architecture. The introduction of ancillary ligands to each of these condensed intermediates caused the weak thioether–metal bonds to break, thus generating a large macrocycle in which the distance between diimide units is significantly larger than for the condensed intermediates. The two Rh^I cationic condensed intermediates were characterized by single‐crystal X‐ray diffraction studies, and the electrochemical activity of these macrocycles was demonstrated with the naphthalene diimide–Cu^I macrocycles.