%0 Journal Article
%A Lensen, Marga C.
%A Nolte, Roeland J. M.
%A Rowan, Alan E.
%A Pyckhout-Hintzen, Wim
%A Feiters, Martin C.
%A Elemans, Johannes A. A. W.
%T Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination
%J Dalton transactions
%V 47
%N 40
%@ 0300-9246
%C London
%I Soc.
%M FZJ-2018-06073
%P 14277 - 14287
%D 2018
%X The 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.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:29881835
%U <Go to ISI:>//WOS:000447708900015
%R 10.1039/C8DT01572D
%U https://juser.fz-juelich.de/record/856722