Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 12, Issue 31, Pages 8136-8149Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200600463
Keywords
N ligands; nanostructures; porphyrinoids; self-assembly; supramolecular chemistry
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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 3a, 4,4'-bipyridine (3b), and 1,4- di azabicyclo [2.2.2] octane (DABCO; 3c), 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.
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