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000856722 1001_ $$00000-0002-5448-6291$$aLensen, Marga C.$$b0
000856722 245__ $$aSelf-assembly of porphyrin hexamers via bidentate metal–ligand coordination
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000856722 520__ $$aThe supramolecular assembly of metal-porphyrin hexamers with bidentate ligands in chloroform solutions is demonstrated by UV/Vis and 1H NMR-titrations, and Small Angle Neutron Scattering (SANS) experiments. Titrations of zinc porphyrin hexamer Zn1 with 1,4-diazabicyclo[2,2,2]octane (DABCO) revealed that at a DABCO/Zn1 molar ratio of 3, intermolecular sandwich complexes are formed, which can be considered as “circular-shaped porphyrin ladders”. These supramolecular complexes further aggregate into larger polymeric stacks, as a result of a combination of cooperativity effects, pi−pi stacking interactions, and chelate effects. The presence of rodlike assemblies in solution, formed by assembly of Zn1 and DABCO, is confirmed by SANS-experiments. Using a model for cylindrical assemblies, curve fitting calculations reveals that rods with an average length of 26 nm and a radius of 30-35 Å were formed, corresponding to columnar stacks of approximately 30 hexamer molecules. In contrast, the metal-free hexamer H_2 1 did not form extended assemblies due to the absence of coordinative intermolecular interactions.
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000856722 7001_ $$00000-0002-5612-7815$$aNolte, Roeland J. M.$$b1
000856722 7001_ $$0P:(DE-HGF)0$$aRowan, Alan E.$$b2
000856722 7001_ $$0P:(DE-Juel1)130902$$aPyckhout-Hintzen, Wim$$b3
000856722 7001_ $$00000-0003-0130-835X$$aFeiters, Martin C.$$b4$$eCorresponding author
000856722 7001_ $$00000-0003-3825-7218$$aElemans, Johannes A. A. W.$$b5$$eCorresponding author
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