From Supramolecular Porphyrin Tweezers to Dynamic A n B m C l D k Multiporphyrin Arrangements Through Orthogonal Coordination

A dynamic, supramolecular, three‐component A n B m C l bis(zinc porphyrin) tweezer has been prepared quantitatively using the heteroleptic bisphenanthroline (HETPHEN) concept. Upon addition of nitrogenous spacers of different length, namely, the extended bipyridine 3 a , 4,4′‐bipyridine ( 3 b ), and 1,4‐diazabicyclo[2.2.2]octane (DABCO; 3 c ), to set up an additional orthogonal binding motif (Zn Por –N spacer ), three structurally different, still dynamic, four‐component A n B m C l D k assemblies were cleanly formed, as indicated by UV/Vis and NMR titrations as well as by DOSY investigations. The structures were identified as a bridged monotweezer A 2 BC 2 D, a doubly bridged double tweezer A 4 B 2 C 4 D 2 , and a triply bridged double tweezer A 4 B 2 C 4 D 3 , the latter resembling a porphyrin stack. Notably, the same structures were equally formed directly from a mixture of the constituents A, B, C, and D put together in any sequence if the correct stoichiometry was applied.